Complex organic molecules in organic-poor massive young stellar objects

DEFF Research Database (Denmark)

Fayolle, Edith C.; Öberg, Karin I.; Garrod, Robin T.

2015-01-01

to search for complex organic molecules over 8-16 GHz in the 1 mm atmospheric window toward three MYSOs with known ice abundances, but without luminous molecular hot cores. Results. Complex molecules are detected toward all three sources at comparable abundances with respect to CH3OH to classical hot core......Context. Massive young stellar objects (MYSOs) with hot cores are classic sources of complex organic molecules. The origins of these molecules in such sources, as well as the small-and large-scale differentiation between nitrogen-and oxygen-bearing complex species, are poorly understood. Aims. We...... aim to use complex molecule abundances toward a chemically less explored class of MYSOs with weak hot organic emission lines to constrain the impact of hot molecular cores and initial ice conditions on the chemical composition toward MYSOs. Methods. We use the IRAM 30 m and the Submillimeter Array...

Nanoscale contacts to organic molecules based on layered semiconductor substrates

Energy Technology Data Exchange (ETDEWEB)

Strobel, Sebastian

2009-06-15

This work reports on the integration of organic molecules as nanoelectronic device units on semiconductor substrates. Two novel preparation methods for sub-10-nm separated metal electrodes are presented using current microelectronics process technology. The first method utilises AlGaAs/GaAs heterostructures grown by molecular beam epitaxy (MBE) as mold to create planar metal electrodes employing a newly developed, high resolution nanotransfer printing (nTP) process. The second method uses commercially available Silicon-on-Insulator (SOI) substrates as base material for the fabrication of nanogap electrode devices. This sandwich-like material stack consists of a silicon substrate, a thin silicon oxide layer, and a capping silicon layer on top. Electronic transport measurements verified their excellent electrical properties at liquid helium temperatures. Specifically tailored nanogap devices featured an electrode insulation in the GW range even up to room temperature as well as within aqueous electrolyte solution. Finally, the well defined layer architecture facilitated the fabrication of electrodes with gap separations below-10-nm to be directly bridged by molecules. Approximately 12-nm-long conjugated molecules with extended -electron system were assembled onto the devices from solution. A large conductance gap was observed with a steep increase in current at a bias voltage of V{sub T}{approx}{+-}1.5 V. Theoretical calculations based on density functional theory and non-equilibrium Green's function formalism confirmed the measured non-linear IV-characteristics qualitatively and lead to the conclusion that the conductance gap mainly originates from the oxygen containing linker. Temperature dependent investigations of the conductance indicated a hopping charge transport mechanism through the central part of the molecule for bias voltages near but below V{sub T}. (orig.)

Organic Optoelectronic Devices Employing Small Molecules

Science.gov (United States)

Fleetham, Tyler Blain

Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, DeltaE DA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt

Maintained expression of the planar cell polarity molecule Vangl2 and reformation of hair cell orientation in the regenerating inner ear.

Science.gov (United States)

Warchol, Mark E; Montcouquiol, Mireille

2010-09-01

The avian inner ear possesses a remarkable ability to regenerate sensory hair cells after ototoxic injury. Regenerated hair cells possess phenotypes and innervation that are similar to those found in the undamaged ear, but little is known about the signaling pathways that guide hair cell differentiation during the regenerative process. The aim of the present study was to examine the factors that specify the orientation of hair cell stereocilia bundles during regeneration. Using organ cultures of the chick utricle, we show that hair cells are properly oriented after having regenerated entirely in vitro and that orientation is not affected by surgical removal of the striolar reversal zone. These results suggest that the orientation of regenerating stereocilia is not guided by the release of a diffusible morphogen from the striolar reversal zone but is specified locally within the regenerating sensory organ. In order to determine the nature of the reorientation cues, we examined the expression patterns of the core planar cell polarity molecule Vangl2 in the normal and regenerating utricle. We found that Vangl2 is asymmetrically expressed on cells within the sensory epithelium and that this expression pattern is maintained after ototoxic injury and throughout regeneration. Notably, treatment with a small molecule inhibitor of c-Jun-N-terminal kinase disrupted the orientation of regenerated hair cells. Both of these results are consistent with the hypothesis that noncanonical Wnt signaling guides hair cell orientation during regeneration.

Pentaatomic planar tetracoordinate carbon molecules [XCAl(3)](q) [(X,q) = (B,-2), (C,-1), (N,0)] with C-X multiple bonding.

Science.gov (United States)

Cui, Zhong-Hua; Shao, Chang-Bin; Gao, Si-Meng; Ding, Yi-Hong

2010-11-07

Among the fascinating planar tetracoordinate carbon (ptC) species, pentaatomic molecules belong to the smallest class, well-known as "pptC". It has been generally accepted that the planarity of pptC structure is realized via the "delocalization" of the p(z) lone pair at the central carbon and the ligand-ligand bonding interaction. Although "localization" is as key driving force in organic chemistry as "delocalization", the "localization" concept has not been applied to the design of pptC molecules, to the best of our knowledge. In this paper, we apply the "localization" strategy to design computationally a series of new pptC. It is shown that the central carbon atom and one "electronegative" ligand atom X (compared to the Al ligand) effectively form a highly localized C-X multiple bond, converting the lone pair at the central carbon to a two-center two-electron π-bond. At the aug-cc-pVTZ-B3LYP, MP2 and CCSD(T) levels, the designed 18-valence-electron pptC species [XCAl(3)](q); [(X,q) = (B,-2), (C,-1), (N,0)] are found to each possess a stable ptC structure bearing a C-X double bond, indicated by the structural, molecular orbital, Wiberg bonding, potential energy surface and Born-Oppenheimer molecular dynamics (BOMD) analysis. Moreover, our OVGF calculations showed that the presently disclosed (yet previously unconsidered) pptC structure of [C(2)Al(3)](-) could well account for the observed photoelectron spectrum (previously only ascribed to a close-energy fan-like structure). Therefore, [C(2)Al(3)](-) could be the first pptC that bears the highly localized C-X double bond that has been experimentally generated. Notably, the pptC structure is the respective global minimum point for [BCAl(3)](2-) and [NCAl(3)], and the counterion(s) would further stabilize [BCAl(3)](2-) and [C(2)Al(3)](-). Thus, these newly designed pptC species with interesting bonding structure should be viable for future experimental characterization. The presently applied "localization" approach

Organic- and molecule-based magnets

Indian Academy of Sciences (India)

The discovery of organic- and molecule-based magnets has led to design and synthesis of several families with magnetic ordering temperatures as high as ∼ 125° C. Examples of soft and hard magnets with coercivities as high as 27 kOe have also been reported. Examples from our laboratory of organic-based magnets ...

Organic Molecules in Meteorites

Science.gov (United States)

Martins, Zita

2015-08-01

Carbonaceous meteorites are primitive samples from the asteroid belt, containing 3-5wt% organic carbon. The exogenous delivery of organic matter by carbonaceous meteorites may have contributed to the organic inventory of the early Earth. The majority (>70%) of the meteoritic organic material consist of insoluble organic matter (IOM) [1]. The remaining meteoritic organic material (meteorites contain soluble organic molecules with different abundances and distributions, which may reflect the extension of aqueous alteration or thermal metamorphism on the meteorite parent bodies. Extensive aqueous alteration on the meteorite parent body may result on 1) the decomposition of α-amino acids [5, 6]; 2) synthesis of β- and γ-amino acids [2, 6-9]; 3) higher relative abundances of alkylated polycyclic aromatic hydrocarbons (PAHs) [6, 10]; and 4) higher L-enantiomer excess (Lee) value of isovaline [6, 11, 12].The soluble organic content of carbonaceous meteorites may also have a contribution from Fischer-Tropsch/Haber-Bosch type gas-grain reactions after the meteorite parent body cooled to lower temperatures [13, 14].The analysis of the abundances and distribution of the organic molecules present in meteorites helps to determine the physical and chemical conditions of the early solar system, and the prebiotic organic compounds available on the early Earth.[1] Cody and Alexander (2005) GCA 69, 1085. [2] Cronin and Chang (1993) in: The Chemistry of Life’s Origin. pp. 209-258. [3] Martins and Sephton (2009) in: Amino acids, peptides and proteins in organic chemistry. pp. 1-42. [4] Martins (2011) Elements 7, 35. [5] Botta et al. (2007) MAPS 42, 81. [6] Martins et al. (2015) MAPS, in press. [7] Cooper and Cronin (1995) GCA 59, 1003. [8] Glavin et al. (2006) MAPS. 41, 889. [9] Glavin et al. (2011) MAPS 45, 1948. [10] Elsila et al. (2005) GCA 5, 1349. [11] Glavin and Dworkin (2009) PNAS 106, 5487. [12] Pizzarello et al. (2003) GCA 67, 1589. [13] Chan et al. (2012) MAPS. 47, 1502

Toxicology of organic-inorganic hybrid molecules: bio-organometallics and its toxicology.

Science.gov (United States)

Fujie, Tomoya; Hara, Takato; Kaji, Toshiyuki

2016-01-01

Bio-organometallics is a research strategy of biology that uses organic-inorganic hybrid molecules. The molecules are expected to exhibit useful bioactivities based on the unique structure formed by interaction between the organic structure and intramolecular metal(s). However, studies on both biology and toxicology of organic-inorganic hybrid molecules have been incompletely performed. There can be two types of toxicological studies of bio-organometallics; one is evaluation of organic-inorganic hybrid molecules and the other is analysis of biological systems from the viewpoint of toxicology using organic-inorganic hybrid molecules. Our recent studies indicate that cytotoxicity of hybrid molecules containing a metal that is nontoxic in inorganic forms can be more toxic than that of hybrid molecules containing a metal that is toxic in inorganic forms when the structure of the ligand is the same. Additionally, it was revealed that organic-inorganic hybrid molecules are useful for analysis of biological systems important for understanding the toxicity of chemical compounds including heavy metals.

Two-photon Photoemission of Organic Semiconductor Molecules on Ag(111)

Energy Technology Data Exchange (ETDEWEB)

Yang, Aram [Univ. of California, Berkeley, CA (United States)

2008-05-01

Angle- and time-resolved two-photon photoemission (2PPE) was used to study systems of organic semiconductors on Ag(111). The 2PPE studies focused on electronic behavior specific to interfaces and ultrathin films. Electron time dynamics and band dispersions were characterized for ultrathin films of a prototypical n-type planar aromatic hydrocarbon, PTCDA, and representatives from a family of p-type oligothiophenes.In PTCDA, electronic behavior was correlated with film morphology and growth modes. Within a fewmonolayers of the interface, image potential states and a LUMO+1 state were detected. The degree to which the LUMO+1 state exhibited a band mass less than a free electron mass depended on the crystallinity of the layer. Similarly, image potential states were measured to have free electron-like effective masses on ordered surfaces, and the effective masses increased with disorder within the thin film. Electron lifetimes were correlated with film growth modes, such that the lifetimes of electrons excited into systems created by layer-by-layer, amorphous film growth increased by orders of magnitude by only a few monolayers from the surface. Conversely, the decay dynamics of electrons in Stranski-Krastanov systems were limited by interaction with the exposed wetting layer, which limited the barrier to decay back into the metal.Oligothiophenes including monothiophene, quaterthiophene, and sexithiophene were deposited on Ag(111), and their electronic energy levels and effective masses were studied as a function of oligothiophene length. The energy gap between HOMO and LUMO decreased with increasing chain length, but effective mass was found to depend on domains from high- or low-temperature growth conditions rather than chain length. In addition, the geometry of the molecule on the surface, e.g., tilted or planar, substantially affected the electronic structure.

Fascinating Organic Molecules from Nature

Indian Academy of Sciences (India)

Home; Journals; Resonance – Journal of Science Education; Volume 18; Issue 5. Fascinating Organic Molecules from Nature - Using a Natural ... Road Banashankari 2nd Stage Bangalore 560 070, India. Department of Chemistry Sri Sathya Sai Institute of Higher Learning Brindavan Campus Bangalore 560 067, India.

Fascinating Organic Molecules from Nature

Indian Academy of Sciences (India)

Home; Journals; Resonance – Journal of Science Education; Volume 18; Issue 7. Fascinating Organic Molecules from Nature - Sweet Stimulants of ... Road Banashankari 2nd Stage Bangalore 560 070, India. Department of Chemistry Sri Sathya Sai Institute of Higher Learning Brindavan Campus Bangalore 560 067, India.

Force microscopy on insulators: imaging of organic molecules

International Nuclear Information System (INIS)

Pfeiffer, O; Gnecco, E; Zimmerli, L; Maier, S; Meyer, E; Nony, L; Bennewitz, R; Diederich, F; Fang, H; Bonifazi, D

2005-01-01

So far, most of the high resolution scanning probe microscopy studies of organic molecules were restricted to metallic substrates. Insulating substrates are mandatory when the molecules need to be electrically decoupled in a electronic circuit. In such a case, atomic force microscopy is required. In this paper we will discuss our recent studies on different organic molecules deposited on KBr surfaces in ultra-high vacuum, and then imaged by AFM at room temperature. The distance between tip and surface was controlled either by the frequency-shift of the cantilever resonance or by the excitation signal required to keep the oscillation amplitude constant. Advantages and drawbacks of both techniques are discussed. The high mobility of the molecules, due to their weak interaction with the substrate, hinders the formation of regular self assembled structures. To overcome this problem we created artificial structures on the surface by annealing and by electron irradiation, which made possible the growth of the molecules onto step edges and their confinement into rectangular pits

Effect of organic molecules on hydrolysis of peptide bond: A DFT study

International Nuclear Information System (INIS)

Makshakova, Olga; Ermakova, Elena

2013-01-01

Highlights: ► DFT study of the effects of small organic molecules on the hydrolysis reactions of peptide bonds. ► Organic molecules can activate nonenzymatic hydrolysis reaction. ► Influence of organic acids on activation energy barrier correlates with their electronegativity. - Abstract: The activation and inhibition effects of small organic molecules on peptide hydrolysis have been studied using a model compound dialanine and DFT approach. Solvent-assisted and non-assisted concerted mechanisms were analyzed. Several transition states for the systems: alanine dipeptide–water molecule in complexes with alcohol molecules, acetonitrile, dimethylsulfoxide, propionic, lactic and pyruvic acids and water molecules were localized. The formation of hydrogen bonds between dipeptide, reactive water molecule and molecules of solvents influences the activation energy barrier of the peptide bond hydrolytic reaction. Strong effect of organic acids on the activation energy barrier correlates with their electronegativity. Acetonitrile can act as an inhibitor of reaction. Mechanisms of regulation of the activation energy barrier are discussed in the terms of donor-acceptor interactions

Nanodevices for generating power from molecules and batteryless sensing

Energy Technology Data Exchange (ETDEWEB)

Wang, Yinmin; Wang, Xianying; Hamza, Alex V.

2017-01-03

A nanoconverter or nanosensor is disclosed capable of directly generating electricity through physisorption interactions with molecules that are dipole containing organic species in a molecule interaction zone. High surface-to-volume ratio semiconductor nanowires or nanotubes (such as ZnO, silicon, carbon, etc.) are grown either aligned or randomly-aligned on a substrate. Epoxy or other nonconductive polymers are used to seal portions of the nanowires or nanotubes to create molecule noninteraction zones. By correlating certain molecule species to voltages generated, a nanosensor may quickly identify which species is detected. Nanoconverters in a series parallel arrangement may be constructed in planar, stacked, or rolled arrays to supply power to nano- and micro-devices without use of external batteries. In some cases breath, from human or other life forms, contain sufficient molecules to power a nanoconverter. A membrane permeable to certain molecules around the molecule interaction zone increases specific molecule nanosensor selectivity response.

X-ray characterization of solid small molecule organic materials

Science.gov (United States)

Billinge, Simon; Shankland, Kenneth; Shankland, Norman; Florence, Alastair

2014-06-10

The present invention provides, inter alia, methods of characterizing a small molecule organic material, e.g., a drug or a drug product. This method includes subjecting the solid small molecule organic material to x-ray total scattering analysis at a short wavelength, collecting data generated thereby, and mathematically transforming the data to provide a refined set of data.

Organic molecules with abnormal geometric parameters

International Nuclear Information System (INIS)

Komarov, Igor V

2001-01-01

Organic molecules, the structural parameters of which (carbon-carbon bond lengths, bond and torsion angles) differ appreciably from the typical most frequently encountered values, are discussed. Using many examples of 'record-breaking' molecules, the limits of structural distortions in carbon compounds and their unusual chemical properties are demonstrated. Particular attention is devoted to strained compounds not yet synthesised whose properties have been predicted using quantum-chemical calculations. Factors that ensure the stability of such compounds are outlined. The bibliography includes 358 references.

Planar waveguides and other confined geometries theory, technology, production, and novel applications

CERN Document Server

2015-01-01

This book provides a comprehensive overview of the theoretical concepts and experimental applications of planar waveguides and other confined geometries, such as optical fibres. Covering a broad array of advanced topics, it begins with a sophisticated discussion of planar waveguide theory, and covers subjects including efficient production of planar waveguides, materials selection, nonlinear effects, and applications including species analytics down to single-molecule identification, and thermo-optical switching using planar waveguides. Written by specialists in the techniques and applications covered, this book will be a useful resource for advanced graduate students and researchers studying planar waveguides and optical fibers.

On the tautomerism, planarity, and vibrations of phospholes

International Nuclear Information System (INIS)

Oziminski, Wojciech P.; Dobrowolski, Jan Cz.

2005-01-01

The PH and CH tautomers of mono-, di-, tri-, tetra-, and pentaphospholes were calculated at the B3LYP/aug-cc-pVTZ level. Except for 1,2,3-triphosphole and pentaphosphole, the most stable phosphole form is one of the CH tautomers. For 1,2-diphosphole, 1,3-diphosphole, and 1,2,4-triphosphole, the energy difference between the tautomers is large and only one tautomer may be observed. For other phospholes, especially tetraphosphole, two tautomers may coexist. Non-planarity of the five membered ring is present only in the σ 3 λ 3 -P atom containing molecules, i.e., PH type of tautomers, while in the CH type of tautomers the ring is planar. As earlier reported by Nyulaszi, the PH tautomers flatten, and the energy difference between PH phosphole and the planar transition state structure decreases, as the number of P atoms in the phosphole molecule is increased. Bond length changes were discussed in terms of configuration of the atoms attached to the bond, and the molecular frequency variations were examined according to the different surroundings of the appropriate vibrators

Comparison of conventional, model-based quantitative planar, and quantitative SPECT image processing methods for organ activity estimation using In-111 agents

International Nuclear Information System (INIS)

He, Bin; Frey, Eric C

2006-01-01

Accurate quantification of organ radionuclide uptake is important for patient-specific dosimetry. The quantitative accuracy from conventional conjugate view methods is limited by overlap of projections from different organs and background activity, and attenuation and scatter. In this work, we propose and validate a quantitative planar (QPlanar) processing method based on maximum likelihood (ML) estimation of organ activities using 3D organ VOIs and a projector that models the image degrading effects. Both a physical phantom experiment and Monte Carlo simulation (MCS) studies were used to evaluate the new method. In these studies, the accuracies and precisions of organ activity estimates for the QPlanar method were compared with those from conventional planar (CPlanar) processing methods with various corrections for scatter, attenuation and organ overlap, and a quantitative SPECT (QSPECT) processing method. Experimental planar and SPECT projections and registered CT data from an RSD Torso phantom were obtained using a GE Millenium VH/Hawkeye system. The MCS data were obtained from the 3D NCAT phantom with organ activity distributions that modelled the uptake of 111 In ibritumomab tiuxetan. The simulations were performed using parameters appropriate for the same system used in the RSD torso phantom experiment. The organ activity estimates obtained from the CPlanar, QPlanar and QSPECT methods from both experiments were compared. From the results of the MCS experiment, even with ideal organ overlap correction and background subtraction, CPlanar methods provided limited quantitative accuracy. The QPlanar method with accurate modelling of the physical factors increased the quantitative accuracy at the cost of requiring estimates of the organ VOIs in 3D. The accuracy of QPlanar approached that of QSPECT, but required much less acquisition and computation time. Similar results were obtained from the physical phantom experiment. We conclude that the QPlanar method, based

Desorption of large organic molecules by laser-induced plasmon excitation

International Nuclear Information System (INIS)

Lee, I.; Callcott, T.A.

1991-01-01

Ejection of large organic molecules from surfaces by laser-induced electronic-excited desorption has attracted considerable interest in recent years. In addition to the importance of this effect for fundamental investigations of the ejection process, this desorption technique has been applied to the study of large, fragile molecules by mass spectrometry. In this paper, we present a new method to induce electronic excitation on the metal surface for the desorption of large organic molecules. 3 refs., 3 figs

Work-Function and Surface Energy Tunable Cyanoacrylic Acid Small-Molecule Derivative Interlayer on Planar ZnO Nanorods for Improved Organic Photovoltaic Performance.

Science.gov (United States)

Ambade, Swapnil B; Ambade, Rohan B; Bagde, Sushil S; Lee, Soo-Hyoung

2016-12-28

The issue of work-function and surface energy is fundamental to "decode" the critical inorganic/organic interface in hybrid organic photovoltaics, which influences important photovoltaic events like exciton dissociation, charge transfer, photocurrent (J sc ), open-circuit voltage (V oc ), etc. We demonstrate that by incorporating an interlayer of cyanoacrylic acid small molecular layer (SML) on solution-processed, spin-coated, planar ZnO nanorods (P-ZnO NRs), higher photovoltaic (PV) performances were achieved in both inverted organic photovoltaic (iOPV) and hybrid organic photovoltaic (HOPV) devices, where ZnO acts as an "electron-transporting layer" and as an "electron acceptor", respectively. For the tuned range of surface energy from 52.5 to 33 mN/m, the power conversion efficiency (PCE) in bulk heterojunction (BHJ) iOPVs based on poly(3-hexylthiophene) (P3HT) and phenyl-C 60 -butyric acid methyl ester (PC 60 BM) increases from 3.16% to 3.68%, and that based on poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2-6-diyl)] (PTB7:Th):[6,6]-phenyl C 71 butyric acid methyl ester (PC 71 BM) photoactive BHJ increases from 6.55% to 8.0%, respectively. The improved PV performance in iOPV devices is majorly attributed to enhanced photocurrents achieved as a result of reduced surface energy and greater electron affinity from the covalent attachment of the strong electron-withdrawing cyano moiety, while that in HOPV devices, where PCE increases from 0.21% to 0.79% for SML-modified devices, is ascribed to a large increase in V oc benefitted due to reduced work function effected from the presence of strong dipole moment in SML that points away from P-ZnO NRs.

Fabrication of combinatorial nm-planar electrode array for high throughput evaluation of organic semiconductors

International Nuclear Information System (INIS)

Haemori, M.; Edura, T.; Tsutsui, K.; Itaka, K.; Wada, Y.; Koinuma, H.

2006-01-01

We have fabricated a combinatorial nm-planar electrode array by using photolithography and chemical mechanical polishing processes for high throughput electrical evaluation of organic devices. Sub-nm precision was achieved with respect to the average level difference between each pair of electrodes and a dielectric layer. The insulating property between the electrodes is high enough to measure I-V characteristics of organic semiconductors. Bottom-contact field-effect-transistors (FETs) of pentacene were fabricated on this electrode array by use of molecular beam epitaxy. It was demonstrated that the array could be used as a pre-patterned device substrate for high throughput screening of the electrical properties of organic semiconductors

Conformal, planarizing and bridging AZ5214-E layers deposited by a 'draping' technique on non-planar III V substrates

Science.gov (United States)

Eliás, P.; Strichovanec, P.; Kostic, I.; Novák, J.

2006-12-01

A draping technique was tested for the deposition of positive-tone AZ5214-E photo-resist layers on non-planar (1 0 0)-oriented III-V substrates, which had a variety of three-dimensional (3D) topographies micromachined in them that consisted, e.g., of mesa ridges confined to side facets with variable tilt, inverted pyramidal holes and stubs confined to perpendicular side facets. All objects were sharp-edged. In each draping experiment, an AZ5214-E sheet was (1) formed floating on the water surface, (2) lowered onto a non-planar substrate and (3) draped over it during drying to form either self-sustained, or conformal, or planarizing layers over the non-planar substrates. The draping process is based on the depression of the glass transition temperature Tg of AZ5214-E material induced by penetrant water molecules that interact with AZ5214-E. During the process, the molecules are initially trapped under an AZ5214-E sheet and then transported out through the sheet via permeation. The water-AZ5214-E interaction modifies the stiffness κ of the sheet. The magnitude of the effect depends on temperature T and on partial water vapour pressure difference p(T, P, κ): the net effect is that Tg = f(C(T, P), p(T, P, κ)) is lowered as the concentration C of water increases with T and p, where P is the permeability of the sheet. The interaction depressed the Tg of the sheets as low as or lower than 53 °C for 6 µm thick sheets. At room temperature T Tg, the sheet becomes rubbery and mouldable by adhesion and capillary forces. As a result, it can either contour or planarize the topography depending on its geometry and thickness of the sheet.

Radiation-induced transformations of isolated organic molecules in solid rare gas matrices

International Nuclear Information System (INIS)

Feldman, V.I.

1998-01-01

Complete text of publication follows. The studies of radiation-chemical behaviour of isolated organic molecules in rigid inert media are of considerable interest for radiation chemistry and general structural chemistry. Previous efforts were limited to the ESR studies of radicals resulting from some small hydrocarbon molecules in frozen rare gas solutions. Recently, we developed an approach to the radiation chemistry of isolated organic molecules using classic matrix isolation procedure for sample preparation and a combination of ESR and IR spectroscopy for characterization of paramagnetic and diamagnetic species resulting form electron irradiation or organic molecules in solid rare gas matrices at 10-15 K. The results obtained reveal high efficiency of energy transfer from rare gas matrix to organic molecules. The total radiation-chemical yields of degradation of organic molecules in argon and xenon matrices were measured directly by IR spectroscopy. The studies of the effect of electron scavengers on the radiolysis of organic molecules in solid rare gases show that the main primary process is positive hole transfer from matrix to additive molecule. ESR spectra of a number of radical cations (alkanes, ethers, arenes) were first characterized in a low-disturbing environment. It was found that the electronic characteristics (IP, polarizability) of the matrix used had crucial effect on trapping and degradation of primary organic radical cations. Using matrices with various IP provides an unique possibility to examine the chemical meaning of excess energy resulting from exothermic positive hole transfer, that is, to follow the fate of excited cations in condensed phase

[DNA complexes, formed on aqueous phase surfaces: new planar polymeric and composite nanostructures].

Science.gov (United States)

Antipina, M N; Gaĭnutdinov, R V; Rakhnianskaia, A A; Sergeev-Cherenkov, A N; Tolstikhina, A L; Iurova, T V; Kislov, V V; Khomutov, G B

2003-01-01

The formation of DNA complexes with Langmuir monolayers of the cationic lipid octadecylamine (ODA) and the new amphiphilic polycation poly-4-vinylpyridine with 16% of cetylpyridinium groups (PVP-16) on the surface of an aqueous solution of native DNA of low ionic strength was studied. Topographic images of Langmuir-Blodgett films of DNA/ODA and DNA/PVP-16 complexes applied to micaceous substrates were investigated by the method of atomic force microscopy. It was found that films of the amphiphilic polycation have an ordered planar polycrystalline structure. The morphology of planar DNA complexes with the amphiphilic cation substantially depended on the incubation time and the phase state of the monolayer on the surface of the aqueous DNA solution. Complex structures and individual DNA molecules were observed on the surface of the amphiphilic monolayer. Along with quasi-linear individual bound DNA molecules, characteristic extended net-like structures and quasi-circular toroidal condensed conformations of planar DNA complexes were detected. Mono- and multilayer films of DNA/PVP-16 complexes were used as templates and nanoreactors for the synthesis of inorganic nanostructures via the binding of metal cations from the solution and subsequent generation of the inorganic phase. As a result, ultrathin polymeric composite films with integrated DNA building blocks and quasi-linear arrays of inorganic semiconductor (CdS) and iron oxide nanoparticles and nanowires were obtained. The nanostructures obtained were characterized by scanning probe microscopy and transmission electron microscopy techniques. The methods developed are promising for investigating the mechanisms of structural organization and transformation in DNA and polyelectrolyte complexes at the gas-liquid interface and for the design of new extremely thin highly ordered planar polymeric and composite materials, films, and coatings with controlled ultrastructure for applications in nanoelectronics and

Challenges for single molecule electronic devices with nanographene and organic molecules. Do single molecules offer potential as elements of electronic devices in the next generation?

Science.gov (United States)

Enoki, Toshiaki; Kiguchi, Manabu

2018-03-01

Interest in utilizing organic molecules to fabricate electronic materials has existed ever since organic (molecular) semiconductors were first discovered in the 1950s. Since then, scientists have devoted serious effort to the creation of various molecule-based electronic systems, such as molecular metals and molecular superconductors. Single-molecule electronics and the associated basic science have emerged over the past two decades and provided hope for the development of highly integrated molecule-based electronic devices in the future (after the Si-based technology era has ended). Here, nanographenes (nano-sized graphene) with atomically precise structures are among the most promising molecules that can be utilized for electronic/spintronic devices. To manipulate single small molecules for an electronic device, a single molecular junction has been developed. It is a powerful tool that allows even small molecules to be utilized. External electric, magnetic, chemical, and mechanical perturbations can change the physical and chemical properties of molecules in a way that is different from bulk materials. Therefore, the various functionalities of molecules, along with changes induced by external perturbations, allows us to create electronic devices that we cannot create using current top-down Si-based technology. Future challenges that involve the incorporation of condensed matter physics, quantum chemistry calculations, organic synthetic chemistry, and electronic device engineering are expected to open a new era in single-molecule device electronic technology.

Crystallization of Organic Semiconductor Molecules in Nanosized Cavities

DEFF Research Database (Denmark)

Milita, Silvia; Dionigi, Chiara; Borgatti, Francesco

2008-01-01

The crystallization of an organic semiconductor, viz., tetrahexil-sexithiophene (H4T6) molecules, confined into nanosized cavities of a self-organized polystyrene beads template, has been investigated by means of in situ grazing incidence X-ray diffraction measurements, during the solvent evapora...

Photovoltaic effect on the performance enhancement of organic light-emitting diodes with planar heterojunction architecture

Energy Technology Data Exchange (ETDEWEB)

Zhao, Dan; Huang, Wei; Guo, Hao [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu 610054 (China); Wang, Hua, E-mail: wanghua001@tyut.edu.cn [Research Center of Advanced Materials Science and Technology, Taiyuan University of Technology (TYUT), Taiyuan 030024 (China); Yu, Junsheng, E-mail: jsyu@uestc.edu.cn [State Key Laboratory of Electronic Thin Films and Integrated Devices, School of Optoelectronic Information, University of Electronic Science and Technology of China (UESTC), Chengdu 610054 (China)

2017-04-15

Highlights: • The photovoltaic effect on the performance of OLEDs was studied. • The device performance with different planar heterojunctions was investigated. • The mechanism relies on the overlap of electroluminescence and absorption spectrum. - Abstract: Organic light-emitting diodes (OLEDs) with planar heterojunction (PHJ) architecture consisting of photovoltaic organic materials of fullerene carbon 60 (C{sub 60}) and copper (II) phthalocyanine (CuPc) inserted between emitting unit and cathode were constructed, and the photovoltaic effect on OLEDs performance was studied. The electroluminescent (EL) characteristics and mechanism of device performance variation without and with different PHJs (herein including C{sub 60}/CuPc, CuPc/C{sub 60} and CuPc) were systematically investigated in red, green and blue OLEDs. Of the three combinations, OLEDs with C{sub 60}/CuPc showed the highest efficiency. It is revealed that the photovoltaic C{sub 60}/CuPc PHJ can absorb part of photons, which are radiated from emission zone, then form excitons, and dissociated into free charges. Consequently, the high device efficiency of OLEDs performance improvement was acquired. This research demonstrates that PHJ consisting of two n- and p-type photovoltaic organic materials could be a promising methodology for high performance OLEDs.

Photovoltaic effect on the performance enhancement of organic light-emitting diodes with planar heterojunction architecture

International Nuclear Information System (INIS)

Zhao, Dan; Huang, Wei; Guo, Hao; Wang, Hua; Yu, Junsheng

2017-01-01

Highlights: • The photovoltaic effect on the performance of OLEDs was studied. • The device performance with different planar heterojunctions was investigated. • The mechanism relies on the overlap of electroluminescence and absorption spectrum. - Abstract: Organic light-emitting diodes (OLEDs) with planar heterojunction (PHJ) architecture consisting of photovoltaic organic materials of fullerene carbon 60 (C_6_0) and copper (II) phthalocyanine (CuPc) inserted between emitting unit and cathode were constructed, and the photovoltaic effect on OLEDs performance was studied. The electroluminescent (EL) characteristics and mechanism of device performance variation without and with different PHJs (herein including C_6_0/CuPc, CuPc/C_6_0 and CuPc) were systematically investigated in red, green and blue OLEDs. Of the three combinations, OLEDs with C_6_0/CuPc showed the highest efficiency. It is revealed that the photovoltaic C_6_0/CuPc PHJ can absorb part of photons, which are radiated from emission zone, then form excitons, and dissociated into free charges. Consequently, the high device efficiency of OLEDs performance improvement was acquired. This research demonstrates that PHJ consisting of two n- and p-type photovoltaic organic materials could be a promising methodology for high performance OLEDs.

Prediction of Physicochemical Properties of Organic Molecules Using Semi-Empirical Methods

International Nuclear Information System (INIS)

Kim, Chan Kyung; Kim, Chang Kon; Kim, Miri; Lee, Hai Whang; Cho, Soo Gyeong

2013-01-01

Prediction of physicochemical properties of organic molecules is an important process in chemistry and chemical engineering. The MSEP approach developed in our lab calculates the molecular surface electrostatic potential (ESP) on van der Waals (vdW) surfaces of molecules. This approach includes geometry optimization and frequency calculation using hybrid density functional theory, B3LYP, at the 6-31G(d) basis set to find minima on the potential energy surface, and is known to give satisfactory QSPR results for various properties of organic molecules. However, this MSEP method is not applicable to screen large database because geometry optimization and frequency calculation require considerable computing time. To develop a fast but yet reliable approach, we have re-examined our previous work on organic molecules using two semi-empirical methods, AM1 and PM3. This new approach can be an efficient protocol in designing new molecules with improved properties

Efficient small molecule bulk heterojunction solar cells with high fill factors via pyrene-directed molecular self-assembly

KAUST Repository

Lee, Olivia P.; Yiu, Alan T.; Beaujuge, Pierre; Woo, Claire; Holcombe, Thomas W.; Millstone, Jill E.; Douglas, Jessica D.; Chen, Mark S.; Frechet, Jean

2011-01-01

Efficient organic photovoltaic (OPV) materials are constructed by attaching completely planar, symmetric end-groups to donor-acceptor electroactive small molecules. Appending C2-pyrene as the small molecule end-group to a diketopyrrolopyrrole core leads to materials with a tight, aligned crystal packing and favorable morphology dictated by π-π interactions, resulting in high power conversion efficiencies and high fill factors. The use of end-groups to direct molecular self-assembly is an effective strategy for designing high-performance small molecule OPV devices. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient small molecule bulk heterojunction solar cells with high fill factors via pyrene-directed molecular self-assembly

KAUST Repository

Lee, Olivia P.

2011-10-21

Efficient organic photovoltaic (OPV) materials are constructed by attaching completely planar, symmetric end-groups to donor-acceptor electroactive small molecules. Appending C2-pyrene as the small molecule end-group to a diketopyrrolopyrrole core leads to materials with a tight, aligned crystal packing and favorable morphology dictated by π-π interactions, resulting in high power conversion efficiencies and high fill factors. The use of end-groups to direct molecular self-assembly is an effective strategy for designing high-performance small molecule OPV devices. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid heterojunction solar cell based on organic-inorganic silicon nanowire array architecture.

Science.gov (United States)

Shen, Xiaojuan; Sun, Baoquan; Liu, Dong; Lee, Shuit-Tong

2011-12-07

Silicon nanowire arrays (SiNWs) on a planar silicon wafer can be fabricated by a simple metal-assisted wet chemical etching method. They can offer an excellent light harvesting capability through light scattering and trapping. In this work, we demonstrated that the organic-inorganic solar cell based on hybrid composites of conjugated molecules and SiNWs on a planar substrate yielded an excellent power conversion efficiency (PCE) of 9.70%. The high efficiency was ascribed to two aspects: one was the improvement of the light absorption by SiNWs structure on the planar components; the other was the enhancement of charge extraction efficiency, resulting from the novel top contact by forming a thin organic layer shell around the individual silicon nanowire. On the contrary, the sole planar junction solar cell only exhibited a PCE of 6.01%, due to the lower light trapping capability and the less hole extraction efficiency. It indicated that both the SiNWs structure and the thin organic layer top contact were critical to achieve a high performance organic/silicon solar cell. © 2011 American Chemical Society

Inorganic-Organic Molecules and Solids with Nanometer-Sized Pores

Energy Technology Data Exchange (ETDEWEB)

Maverick, Andrew W

2011-12-17

We are constructing porous inorganic-organic hybrid molecules and solids, many of which contain coordinatively unsaturated metal centers. In this work, we use multifunctional ²-diketone ligands as building blocks to prepare extended-solid and molecular porous materials that are capable of reacting with a variety of guest molecules.

In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

Science.gov (United States)

Li, Xiang; Brinckerhoff, William B.; Pinnick, Veronica T; van Amerom, Friso H. W.; Danell, Ryan M.; Arevalo, Ricardo D., Jr.; Getty, Stephanie; Mahaffy, Paul R.

2015-01-01

The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds.

Hole-transport limited S-shaped I-V curves in planar heterojunction organic photovoltaic cells

Science.gov (United States)

Zhang, Minlu; Wang, Hui; Tang, C. W.

2011-11-01

Current-voltage (I-V) characteristics of planar heterojunction organic photovoltaic cells based on N',N'-Di-[(1-naphthyl)-N',N'-diphenyl]-1,1'-biphenyl)-4,4'-diamine (NPB) and C60 are investigated. Through variation of the layer thickness and composition, specifically chemical doping NPB with MoOx, we show that the hole-transport limitation in the NPB layer is the determining factor in shaping the I-V characteristics of NPB/C60 cells.

Contact planarization of ensemble nanowires

Science.gov (United States)

Chia, A. C. E.; LaPierre, R. R.

2011-06-01

The viability of four organic polymers (S1808, SC200, SU8 and Cyclotene) as filling materials to achieve planarization of ensemble nanowire arrays is reported. Analysis of the porosity, surface roughness and thermal stability of each filling material was performed. Sonication was used as an effective method to remove the tops of the nanowires (NWs) to achieve complete planarization. Ensemble nanowire devices were fully fabricated and I-V measurements confirmed that Cyclotene effectively planarizes the NWs while still serving the role as an insulating layer between the top and bottom contacts. These processes and analysis can be easily implemented into future characterization and fabrication of ensemble NWs for optoelectronic device applications.

Simultaneous atomization and ionization of large organic molecules using femtosecond laser ablation

International Nuclear Information System (INIS)

Kurata-Nishimura, Mizuki; Tokanai, Fuyuki; Matsuo, Yukari; Kobayashi, Tohru; Kawai, Jun; Kumagai, Hiroshi; Midorikawa, Katsumi; Tanihata, Isao; Hayashizaki, Yoshihide

2002-01-01

We have experimentally demonstrated femtosecond laser ablation for simultaneous atomization and ionization (fs-SAI) of organic molecules on solid substrates. We find most of the constituent atoms of organic molecules are atomized and ionized non-resonantly by femtosecond laser ablation. This observation is in contrast with that for the photoionization of cyclic aromatic hydrocarbons by femtosecond laser in the gas phase where little fragmentation has been observed. Crucial contribution of ablation plasma of solid sample to fs-SAI process is suggested. The ratio of natural abundance of stable isotopes contained in sample molecules is well reproduced, which confirms fs-SAI can be applied to the quantitative chemical analysis of isotope-labeled large organic molecules

Bifunctional Pt-Si Alloys for Small Organic Molecule Electro-oxidation

DEFF Research Database (Denmark)

Permyakova, Anastasia Aleksandrovna; Suntivich, Jin; Han, Binghong

Designing highly active catalysts for electro-oxidation of small organic molecules can help to reduce the anodic overpotential for more efficient utilization of hydrocarbon fuels. The challenge in developing more active electrocatalysts for electro-oxidation reactions is to satisfy the stringent...... adsorption site. We will discuss the enhanced activity of Pt-Si alloys for small organic molecule oxidation, which can be attributed to the improved CO electro-oxidation kinetics on Pt-Si....

Embarras de richesses - It is not good to be too anomalous: Accurate structure of selenourea, a chiral crystal of planar molecules.

Science.gov (United States)

Luo, Zhipu; Dauter, Zbigniew

2017-01-01

Selenourea, SeC(NH2)2, recently found an application as a derivatization reagent providing a significant anomalous diffraction signal used for phasing macromolecular crystal structures. The crystal structure of selenourea itself was solved about 50 years ago, from data recorded on films and evaluated by eye and refined to R = 0.15 with errors of bond lengths and angles about 0.1 Å and 6°. In the current work this structure is re-evaluated on the basis of synchrotron data and refined to R1 = 0.021 with bond and angle errors about 0.007 Å and 0.5°. The nine planar molecules of selenourea pack either in the P31 or in the P32 unit cell. All unique molecules are connected by a complex network of Se•••H-N hydrogen bonds and Se•••Se contacts. The packing of selenourea molecules is highly pseudosymmetric, approximating either of the P31(2)12, R3, and R32 space groups. Because the overwhelming majority of diffracted X-ray intensity originates form the anomalously scattering selenium atoms, the measurable anomalous Bijvoet differences are diminished and it was not possible to solve this crystal structure based on the anomalous signal alone.

Improved Efficiency in Inverted Perovskite Solar Cells Employing a Novel Diarylamino-Substituted Molecule as PEDOT:PSS Replacement

KAUST Repository

El Labban, Abdulrahman

2016-03-15

An approach to fabricate high-efficiency inverted planar perovskites solar cells using solution-processed organic small molecules hole transporting layer is reported. Devices using CH3NH3PbI3 as photoactive layer and PC60BM as electron transport layer show power conversion efficiencies exceeding 12% and open-circuit voltages (VOC) higher than 1 V.

Improved Efficiency in Inverted Perovskite Solar Cells Employing a Novel Diarylamino-Substituted Molecule as PEDOT:PSS Replacement

KAUST Repository

El Labban, Abdulrahman; Chen, Hu; Kirkus, Mindaugas; Barbe, Jeremy; Del Gobbo, Silvano; Neophytou, Marios; McCulloch, Iain; Eid, Jessica

2016-01-01

An approach to fabricate high-efficiency inverted planar perovskites solar cells using solution-processed organic small molecules hole transporting layer is reported. Devices using CH3NH3PbI3 as photoactive layer and PC60BM as electron transport layer show power conversion efficiencies exceeding 12% and open-circuit voltages (VOC) higher than 1 V.

Structure and Structure-activity Relationship of Functional Organic Molecules

Institute of Scientific and Technical Information of China (English)

2011-01-01

@@ Research theme The group is made up of junior scientists from the State Key Laboratory of Elemento-organic Chemistry, Nankai University.The scientists focus their studis on the structure and structure-activity relationship of functional organic molecules not only because it has been the basis of their research, but also because the functional study of organic compounds is now a major scientific issue for organic chemists around the world.

Desorption of large organic molecules induced by keV projectiles

International Nuclear Information System (INIS)

Delcorte, A.; Garrison, B.J.

2001-01-01

In order to understand the emission of organic molecules in sputtering, classical molecular dynamics (MD) is used to model the 5 keV Ar atom bombardment of polystyrene oligomers adsorbed on Ag{1 1 1}. The analysis of the results shows that a significant fraction of the trajectories generates high action events in the sample. These events are characterized by the simultaneous motion of several hundreds of substrate atoms and, oftentimes, by high emission yields of substrate atoms, clusters and polystyrene molecules. Collision trees representing the energetic part of the cascades confirm that high sputtering yields of molecules occur when a large portion of the primary particle energy is quickly dissipated in the upper layers of the silver substrate. This class of events where high action occurs in the surface region might explain the ejection of organic species with a mass of several kilodaltons such as biomolecules and synthetic polymers. In the simulation, these events are capable of desorbing polystyrene molecules of ∼2 kDa

Planar Cell Polarity Breaks the Symmetry of PAR Protein Distribution prior to Mitosis in Drosophila Sensory Organ Precursor Cells.

Science.gov (United States)

Besson, Charlotte; Bernard, Fred; Corson, Francis; Rouault, Hervé; Reynaud, Elodie; Keder, Alyona; Mazouni, Khalil; Schweisguth, François

2015-04-20

During development, cell-fate diversity can result from the unequal segregation of fate determinants at mitosis. Polarization of the mother cell is essential for asymmetric cell division (ACD). It often involves the formation of a cortical domain containing the PAR complex proteins Par3, Par6, and atypical protein kinase C (aPKC). In the fly notum, sensory organ precursor cells (SOPs) divide asymmetrically within the plane of the epithelium and along the body axis to generate two distinct cells. Fate asymmetry depends on the asymmetric localization of the PAR complex. In the absence of planar cell polarity (PCP), SOPs divide with a random planar orientation but still asymmetrically, showing that PCP is dispensable for PAR asymmetry at mitosis. To study when and how the PAR complex localizes asymmetrically, we have used a quantitative imaging approach to measure the planar polarization of the proteins Bazooka (Baz, fly Par3), Par6, and aPKC in living pupae. By using imaging of functional GFP-tagged proteins with image processing and computational modeling, we find that Baz, Par6, and aPKC become planar polarized prior to mitosis in a manner independent of the AuroraA kinase and that PCP is required for the planar polarization of Baz, Par6, and aPKC during interphase. This indicates that a "mitosis rescue" mechanism establishes asymmetry at mitosis in PCP mutants. This study therefore identifies PCP as the initial symmetry-breaking signal for the planar polarization of PAR proteins in asymmetrically dividing SOPs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fabrication of organic-inorganic perovskite thin films for planar solar cells via pulsed laser deposition

Energy Technology Data Exchange (ETDEWEB)

Liang, Yangang; Zhang, Xiaohang; Gong, Yunhui; Shin, Jongmoon; Wachsman, Eric D.; Takeuchi, Ichiro, E-mail: takeuchi@umd.edu [Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20740 (United States); Yao, Yangyi; Hsu, Wei-Lun; Dagenais, Mario [Department of Electrical and Computer Engineering, University of Maryland, College Park, Maryland 20740 (United States)

2016-01-15

We report on fabrication of organic-inorganic perovskite thin films using a hybrid method consisting of pulsed laser deposition (PLD) of lead iodide and spin-coating of methylammonium iodide. Smooth and highly crystalline CH{sub 3}NH{sub 3}PbI{sub 3} thin films have been fabricated on silicon and glass coated substrates with fluorine doped tin oxide using this PLD-based hybrid method. Planar perovskite solar cells with an inverted structure have been successfully fabricated using the perovskite films. Because of its versatility, the PLD-based hybrid fabrication method not only provides an easy and precise control of the thickness of the perovskite thin films, but also offers a straightforward platform for studying the potential feasibility in using other metal halides and organic salts for formation of the organic-inorganic perovskite structure.

Fabrication of organic-inorganic perovskite thin films for planar solar cells via pulsed laser deposition

Directory of Open Access Journals (Sweden)

Yangang Liang

2016-01-01

Full Text Available We report on fabrication of organic-inorganic perovskite thin films using a hybrid method consisting of pulsed laser deposition (PLD of lead iodide and spin-coating of methylammonium iodide. Smooth and highly crystalline CH3NH3PbI3 thin films have been fabricated on silicon and glass coated substrates with fluorine doped tin oxide using this PLD-based hybrid method. Planar perovskite solar cells with an inverted structure have been successfully fabricated using the perovskite films. Because of its versatility, the PLD-based hybrid fabrication method not only provides an easy and precise control of the thickness of the perovskite thin films, but also offers a straightforward platform for studying the potential feasibility in using other metal halides and organic salts for formation of the organic-inorganic perovskite structure.

Series of isostructural planar lanthanide complexes [Ln(III)4(mu3-OH)2(mdeaH)2(piv)8] with single molecule magnet behavior for the Dy4 analogue.

Science.gov (United States)

Abbas, Ghulam; Lan, Yanhua; Kostakis, George E; Wernsdorfer, Wolfgang; Anson, Christopher E; Powell, Annie K

2010-09-06

A series of five isostructural tetranuclear lanthanide complexes of formula [Ln(4)(mu(3)-OH)(2)(mdeaH)(2)(piv)(8)], (mdeaH(2) = N-methyldiethanolamine; piv = pivalate; Ln = Tb (1), Dy (2), Ho (3), Er (4), and Tm (5)) have been synthesized and characterized. These clusters have a planar "butterfly" Ln(4) core. Magnetically, the Ln(III) ions are weakly coupled in all cases; the Dy(4) compound 2 shows Single Molecule Magnet (SMM) behavior.

Tunable optical absorption in silicene molecules

KAUST Repository

Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

2016-01-01

Two-dimensional materials with a tunable band gap that covers a wide range of the solar spectrum hold great promise for sunlight harvesting. For this reason, we investigate the structural, electronic, and optical properties of silicene molecules using time dependent density functional theory. We address the influence of the molecular size, buckling, and charge state as well as that of a dielectric environment. Unlike planar graphene molecules, silicene molecules prefer to form low-buckled structures with strong visible to ultraviolet optical response. We also identify molecular plasmons.

Tunable optical absorption in silicene molecules

KAUST Repository

Mokkath, Junais Habeeb

2016-07-13

Two-dimensional materials with a tunable band gap that covers a wide range of the solar spectrum hold great promise for sunlight harvesting. For this reason, we investigate the structural, electronic, and optical properties of silicene molecules using time dependent density functional theory. We address the influence of the molecular size, buckling, and charge state as well as that of a dielectric environment. Unlike planar graphene molecules, silicene molecules prefer to form low-buckled structures with strong visible to ultraviolet optical response. We also identify molecular plasmons.

Improved Reliability of Small Molecule Organic Solar Cells by Double Anode Buffer Layers

Directory of Open Access Journals (Sweden)

Pao-Hsun Huang

2014-01-01

Full Text Available An optimized hybrid planar heterojunction (PHJ of small molecule organic solar cells (SM-OSCs based on copper phthalocyanine (CuPc as donor and fullerene (C60 as acceptor was fabricated, which obviously enhanced the performance of device by sequentially using both MoO3 and pentacene as double anode buffer layers (ABL, also known as hole extraction layer (HEL. A series of the vacuum-deposited ABL, acting as an electron and exciton blocking layer, were examined for their characteristics in SM-OSCs. The performance and reliability were compared between conventional ITO/ABL/CuPc/C60/BCP/Ag cells and the new ITO/double ABL/CuPc/C60/BCP/Ag cells. The effect on the electrical properties of these materials was also investigated to obtain the optimal thickness of ABL. The comparison shows that the modified cell has an enhanced reliability compared to traditional cells. The improvement of lifetime was attributed to the idea of double layers to prevent humidity and oxygen from diffusing into the active layer. We demonstrated that the interfacial extraction layers are necessary to avoid degradation of device. That is to say, in normal temperature and pressure, a new avenue for the device within double buffer layers has exhibited the highest values of open circuit voltage (Voc, fill factor (FF, and lifetime in this work compared to monolayer of ABL.

Nonadiabatic dynamics of electron injection into organic molecules

International Nuclear Information System (INIS)

Zhu Li-Ping; Qiu Yu; Tong Guo-Ping

2012-01-01

We numerically investigate the injection process of electrons from metal electrodes to one-dimensional organic molecules by combining the extended Su—Schrieffer—Heeger (SSH) model with a nonadiabatic dynamics method. It is found that a match between the Fermi level of electrodes and the highest occupied molecular orbital (HOMO) or the lowest unoccupied molecular orbital (LUMO) of organic molecules can be greatly affected by the length of the organic chains, which has a great impact on electron injection. The correlation between oligomers and electrodes is found to open more efficient channels for electron injection as compared with that in polymer/electrode structures. For oligomer/electrode structures, we show that the Schottky barrier essentially does not affect the electron injection as the electrode work function is smaller than a critical value. This means that the Schottky barrier is pinned for a small work-function electrode. For polymer/electrode structures, we find that it is possible for the Fermi level of electrodes to be pinned to the polaronic level. The condition under which the Fermi level of electrodes exceeds the polaronic level of polymers is shown to not always lead to spontaneous electron transfer from electrodes to polymers. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Evidence of thermal transport anisotropy in stable glasses of vapor deposited organic molecules

Science.gov (United States)

Ràfols-Ribé, Joan; Dettori, Riccardo; Ferrando-Villalba, Pablo; Gonzalez-Silveira, Marta; Abad, Llibertat; Lopeandía, Aitor F.; Colombo, Luciano; Rodríguez-Viejo, Javier

2018-03-01

Vapor deposited organic glasses are currently in use in many optoelectronic devices. Their operation temperature is limited by the glass transition temperature of the organic layers and thermal management strategies become increasingly important to improve the lifetime of the device. Here we report the unusual finding that molecular orientation heavily influences heat flow propagation in glassy films of small molecule organic semiconductors. The thermal conductivity of vapor deposited thin-film semiconductor glasses is anisotropic and controlled by the deposition temperature. We compare our data with extensive molecular dynamics simulations to disentangle the role of density and molecular orientation on heat propagation. Simulations do support the view that thermal transport along the backbone of the organic molecule is strongly preferred with respect to the perpendicular direction. This is due to the anisotropy of the molecular interaction strength that limits the transport of atomic vibrations. This approach could be used in future developments to implement small molecule glassy films in thermoelectric or other organic electronic devices.

On the origin of organic molecules in interstellar space and some of its consequences

International Nuclear Information System (INIS)

Johansson, K.L.V.

1981-01-01

The possible sources of complex organic molecules observed in the interstellar space are discussed. It is found that a leakage from lifebearing planets cannot possibly explain the observed amounts of complex organic molecules. They are probably formed in interstellar clouds, either free in space or on the surface of grains. This opens the possibility that planets (also the earth) moving through such clouds may have collected appreciable amounts of complex organic molecules. It would therefore be feasible to perform experiments like the Urey-Miller's, starting with a considerably more complex mixture than the traditional one. (Auth.)

Small organic molecule based flow battery

Science.gov (United States)

Huskinson, Brian; Marshak, Michael; Aziz, Michael J.; Gordon, Roy G.; Betley, Theodore A.; Aspuru-Guzik, Alan; Er, Suleyman; Suh, Changwon

2018-05-08

The invention provides an electrochemical cell based on a new chemistry for a flow battery for large scale, e.g., gridscale, electrical energy storage. Electrical energy is stored chemically at an electrochemical electrode by the protonation of small organic molecules called quinones to hydroquinones. The proton is provided by a complementary electrochemical reaction at the other electrode. These reactions are reversed to deliver electrical energy. A flow battery based on this concept can operate as a closed system. The flow battery architecture has scaling advantages over solid electrode batteries for large scale energy storage.

Structural and electronic properties of single molecules and organic layers on surfaces

NARCIS (Netherlands)

Sotthewes, Kai

2016-01-01

Single molecules and organic layers on well-defined solid surfaces have attracted tremendous attention owing to their interesting physical and chemical properties. The ultimate utility of single molecules or self-assembled monolayers (SAMs) for potential applications is critically dependent on the

Surface functionalization of aluminosilicate nanotubes with organic molecules

Directory of Open Access Journals (Sweden)

Wei Ma

2012-02-01

Full Text Available The surface functionalization of inorganic nanostructures is an effective approach for enriching the potential applications of existing nanomaterials. Inorganic nanotubes attract great research interest due to their one-dimensional structure and reactive surfaces. In this review paper, recent developments in surface functionalization of an aluminosilicate nanotube, “imogolite”, are introduced. The functionalization processes are based on the robust affinity between phosphate groups of organic molecules and the aluminol (AlOH surface of imogolite nanotubes. An aqueous modification process employing a water soluble ammonium salt of alkyl phosphate led to chemisorption of molecules on imogolite at the nanotube level. Polymer-chain-grafted imogolite nanotubes were prepared through surface-initiated polymerization. In addition, the assembly of conjugated molecules, 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-ylethylphosphonic acid (HT3P and 2-(5’’-hexyl-2,2’:5’,2’’-terthiophen-5-ylethylphosphonic acid 1,1-dioxide (HT3OP, on the imogolite nanotube surface was achieved by introducing a phosphonic acid group to the corresponding molecules. The optical and photophysical properties of these conjugated-molecule-decorated imogolite nanotubes were characterized. Moreover, poly(3-hexylthiophene (P3HT chains were further hybridized with HT3P modified imogolite to form a nanofiber hybrid.

Interface properties of organic molecules on metal surfaces; Grenzflaecheneigenschaften organischer Molekuele auf Metalloberflaechen

Energy Technology Data Exchange (ETDEWEB)

Karacuban, Hatice

2010-01-28

In this work, the growth of the archetype molecules CuPc and PTCDA was investigated on Cu(111). PTCDA was also studied on NaCl/Cu(111). The main experiments were carried out with a scanning tunneling microscope. Structural analysis of CuPc on Cu (111) is only possible at low temperatures, since at room temperature the molecules exhibit a high surface mobility. For the investigation of these structures and especially to enable scanning tunneling spectroscopy, a low-temperature scanning tunneling microscope was developed. Using this home built STM the experiments could be carried out at about 10 K. After the adsorption of CuPc on Cu (111) a substrate-induced symmetry reduction of the molecules can be observed in scanning tunneling microscopy. When the occupied states of the molecules are imaged, a switching between two distinct levels is found. These modifications are determined by the adsorption geometry of the molecules. Based on high resolution STM data, an on-top adsorption geometry of the CuPc-molecules on Cu (111)-substrate can be deducted. At low temperatures, two new superstructures of PTCDA on Cu(111) are observed. The molecules within these superstructures are tilted with respect to the substrate. Intermolecular interactions may be the crucial factor for the realignment of the molecules. If PTCDA molecules are adsorbed on a NaCl/Cu (111) substrate, at room temperature, also two new superstructures on the copper substrate were found. They indicate the formation of a metall-organic-complex. On top of the NaCl layer the molecules exclusively grow at polar NaCl step edges. This is an indication for electrostatic interaction between the PTCDA molecules and the NaCl layer. When the molecule density is further increased, a Vollmer-Weber growth sets in. If both molecules PTCDA and CuPc are present on the sample at the same time, local spectroscopy provides information on the metal-organic interface in direct comparison. The STS-results of CuPc/PTCDA on Cu (111

Triton - Stratospheric molecules and organic sediments

Science.gov (United States)

Thompson, W. Reid; Singh, Sushil K.; Khare, B. N.; Sagan, Carl

1989-01-01

Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

Wiener index and Diameter of a Planar Graph in Subquadratic Time

DEFF Research Database (Denmark)

Wulff-Nilsen, Christian

2009-01-01

Consider the problem of computing the sum of distances between each pair of vertices of an unweighted graph. This sum is also known as the Wiener index of the graph, a generalization of a definition given by H. Wiener in 1947. A molecular topological index is a value obtained from the graph...... structure of a molecule such that this value (hopefully) correlates with physical and/or chemical properties of the molecule. The Wiener index is perhaps the most studied molecular topological index with more than a thousand publications. It is open whether the Wiener index of a planar graph can be obtained...... in subquadratic time. In my talk, I will solve this open problem by exhibiting an O(n2 log log n / log n) time algorithm, where n is the size of the graph. A simple modification yields an algorithm with the same time bound that computes the diameter (maximum distance between any vertex pair) of a planar graph. I...

Quantum interference experiments with complex organic molecules

International Nuclear Information System (INIS)

Eibenberger, S. I.

2015-01-01

Matter-wave interference with complex particles is a thriving field in experimental quantum physics. The quest for testing the quantum superposition principle with highly complex molecules has motivated the development of the Kapitza-Dirac-Talbot-Lau interferometer (KDTLI). This interferometer has enabled quantum interference with large organic molecules in an unprecedented mass regime. In this doctoral thesis I describe quantum superposition experiments which we were able to successfully realize with molecules of masses beyond 10 000 amu and consisting of more than 800 atoms. The typical de Broglie wavelengths of all particles in this thesis are in the order of 0.3-5 pm. This is significantly smaller than any molecular extension (nanometers) or the delocalization length in our interferometer (hundreds of nanometers). Many vibrational and rotational states are populated since the molecules are thermally highly excited (300-1000 K). And yet, high-contrast quantum interference patterns could be observed. The visibility and position of these matter-wave interference patterns is highly sensitive to external perturbations. This sensitivity has opened the path to extensive studies of the influence of internal molecular properties on the coherence of their associated matter waves. In addition, it enables a new approach to quantum-assisted metrology. Quantum interference imprints a high-contrast nano-structured density pattern onto the molecular beam which allows us to resolve tiny shifts and dephasing of the molecular beam. I describe how KDTL interferometry can be used to investigate a number of different molecular properties. We have studied vibrationally-induced conformational changes of floppy molecules and permanent electric dipole moments using matter-wave deflectometry in an external electric field. We have developed a new method for optical absorption spectroscopy which uses the recoil of the molecules upon absorption of individual photons. This allows us to

Impact of Thermal Annealing on Organic Photovoltaic Cells Using Regioisomeric Donor-Acceptor-Acceptor Molecules.

Science.gov (United States)

Zhang, Tao; Han, Han; Zou, Yunlong; Lee, Ying-Chi; Oshima, Hiroya; Wong, Ken-Tsung; Holmes, Russell J

2017-08-02

We report a promising set of donor-acceptor-acceptor (D-A-A) electron-donor materials based on coplanar thieno[3,2-b]/[2,3-b]indole, benzo[c][1,2,5]thiadiazole, and dicyanovinylene, which are found to show broadband absorption with high extinction coefficients. The role of the regioisomeric electron-donating thienoindole moiety on the physical and structural properties is examined. Bulk heterojunction (BHJ) organic photovoltaic cells (OPVs) based on the thieno[2,3-b]indole-based electron donor NTU-2, using C 70 as an electron acceptor, show a champion power conversion efficiency of 5.2% under AM 1.5G solar simulated illumination. This efficiency is limited by a low fill factor (FF), as has previously been the case in D-A-A systems. In order to identify the origin of the limited FF, further insight into donor layer charge-transport behavior is realized by examining planar heterojunction OPVs, with emphasis on the evolution of film morphology with thermal annealing. Compared to as-deposited OPVs that exhibit insufficient donor crystallinity, crystalline OPVs based on annealed thin films show an increase in the short-circuit current density, FF, and power conversion efficiency. These results suggest that that the crystallization of D-A-A molecules might not be realized spontaneously at room temperature and that further processing is needed to realize efficient charge transport in these materials.

Characterization of Interstellar Organic Molecules

International Nuclear Information System (INIS)

Gencaga, Deniz; Knuth, Kevin H.; Carbon, Duane F.

2008-01-01

Understanding the origins of life has been one of the greatest dreams throughout history. It is now known that star-forming regions contain complex organic molecules, known as Polycyclic Aromatic Hydrocarbons (PAHs), each of which has particular infrared spectral characteristics. By understanding which PAH species are found in specific star-forming regions, we can better understand the biochemistry that takes place in interstellar clouds. Identifying and classifying PAHs is not an easy task: we can only observe a single superposition of PAH spectra at any given astrophysical site, with the PAH species perhaps numbering in the hundreds or even thousands. This is a challenging source separation problem since we have only one observation composed of numerous mixed sources. However, it is made easier with the help of a library of hundreds of PAH spectra. In order to separate PAH molecules from their mixture, we need to identify the specific species and their unique concentrations that would provide the given mixture. We develop a Bayesian approach for this problem where sources are separated from their mixture by Metropolis Hastings algorithm. Separated PAH concentrations are provided with their error bars, illustrating the uncertainties involved in the estimation process. The approach is demonstrated on synthetic spectral mixtures using spectral resolutions from the Infrared Space Observatory (ISO). Performance of the method is tested for different noise levels.

Adsorption of organic molecules may explain growth of newly nucleated clusters and new particle formation

Science.gov (United States)

Wang, Jian; Wexler, Anthony S.

2013-05-01

New particle formation consists of formation of thermodynamically stable clusters from trace gas molecules (homogeneous nucleation) followed by growth of these clusters to a detectable size. Because of the large coagulation rate of clusters smaller than 3 nm with the preexisting aerosol population, for new particle formation to take place, these clusters need to grow sufficiently fast to escape removal by coagulation. Previous studies have indicated that condensation of low-volatility organic vapor may play an important role in the initial growth of the clusters. However, due to the relatively high vapor pressure and partial molar volume of even highly oxidized organic compounds, the strong Kelvin effect may prevent typical ambient organics from condensing on these small clusters. Earlier studies did not consider that adsorption of organic molecules on the cluster surface, due to the intermolecular forces between the organic molecule and cluster, may occur and substantially alter the growth process under sub-saturated conditions. Using the Brunauer-Emmett-Teller (BET) isotherm, we show that the adsorption of organic molecules onto the surface of clusters may significantly reduce the saturation ratio required for condensation of organics to occur, and therefore may provide a physico-chemical explanation for the enhanced initial growth by condensation of organics despite the strong Kelvin effect.

Effects of Perchlorate on Organic Molecules under Simulated Mars Conditions

Science.gov (United States)

Carrier, B. L.; Kounaves, S. P.

2014-12-01

Perchlorate (ClO4-) was discovered in the northern polar region of Mars by the Mars Phoenix Lander in 2008 and has also been recently detected by the Curiosity Rover in Gale Crater [1,2]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [3]. The discovery of perchlorate on Mars has raised important questions about the effects of perchlorate on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [4], few studies have been conducted on the potential effects of perchlorate on organic molecules under martian surface conditions. Although perchlorate is typically inert under Mars-typical temperatures [5], perchlorate does absorb high energy UV radiation, and has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-) when exposed to martian conditions including UV or ionizing radiation [6,7]. Here we investigate the effects of perchlorate on the organic molecules tryptophan, benzoic acid and mellitic acid in order to determine how perchlorate may alter these compounds under Mars conditions. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of SiO2 and each organic, as well as varying concentrations of perchlorate salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination. References: [1] Kounaves et al., J. Geophys. Res. Planets, Vol. 115, p. E00E10, 2010 [2] Glavin et al., J. Geophys. Res. Planets, Vol

High-performance tandem organic light-emitting diodes based on a buffer-modified p/n-type planar organic heterojunction as charge generation layer

Science.gov (United States)

Wu, Yukun; Sun, Ying; Qin, Houyun; Hu, Shoucheng; Wu, Qingyang; Zhao, Yi

2017-04-01

High-performance tandem organic light-emitting diodes (TOLEDs) were realized using a buffer-modified p/n-type planar organic heterojunction (OHJ) as charge generation layer (CGL) consisting of common organic materials, and the configuration of this p/n-type CGL was "LiF/N,N'-diphenyl-N,N'-bis(1-napthyl)-1,1'-biphenyl-4,4'-diamine (NPB)/4,7-diphenyl-1,10-phenanthroline (Bphen)/molybdenum oxide (MoOx)". The optimized TOLED exhibited a maximum current efficiency of 77.6 cd/A without any out-coupling techniques, and the efficiency roll-off was greatly improved compared to the single-unit OLED. The working mechanism of the p/n-type CGL was discussed in detail. It is found that the NPB/Bphen heterojunction generated enough charges under a forward applied voltage and the carrier extraction was a tunneling process. These results could provide a new method to fabricate high-performance TOLEDs.

Stability of organic molecules against shocks in the young Solar nebula

NARCIS (Netherlands)

Kamp, Inga; Milosavljevic, Milica; Stempels, E

2009-01-01

One of the fundamental astrobiology questions is how life has formed in our Solar System. In this context the formation and stability of abiotic organic molecules such as CH(4), formic acid and amino acids, is important for understanding how organic material has formed and survived shocks and

A Self-Perpetuating Catalyst for the Production of Complex Organic Molecules in Protostellar Nebulae

Science.gov (United States)

Nuth, Joseph A.; Johnson, N. M.

2010-01-01

The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. Many mechanisms may contribute to the total organic content in protostellar nebulae, ranging from organics formed via ion-molecule and atom-molecule reactions in the cold dark clouds from which such nebulae collapse, to similar ion-molecule and atom-molecule reactions in the dark regions of the nebula far from the proto star, to gas phase reactions in sub-nebulae around growing giant planets and in the nebulae themselves. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. The Haber-Bosch catalytic reduction of N2 by hydrogen was thought to produce the reduced nitrogen found in meteorites. However, the clean iron metal surfaces that catalyze these reactions are easily poisoned via reaction with any number of molecules, including the very same complex organics that they produce and both reactions work more efficiently in the hot regions of the nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Although none work as well as pure iron grains, and all produce a wide range of organic products rather than just pure methane, these materials are not truly catalysts.

Organization of central synapses by adhesion molecules.

Science.gov (United States)

Tallafuss, Alexandra; Constable, John R L; Washbourne, Philip

2010-07-01

Synapses are the primary means for transmitting information from one neuron to the next. They are formed during the development of the nervous system, and the formation of appropriate synapses is crucial for the establishment of neuronal circuits that underlie behavior and cognition. Understanding how synapses form and are maintained will allow us to address developmental disorders such as autism, mental retardation and possibly also psychological disorders. A number of biochemical and proteomic studies have revealed a diverse and vast assortment of molecules that are present at the synapse. It is now important to untangle this large array of proteins and determine how it assembles into a functioning unit. Here we focus on recent reports describing how synaptic cell adhesion molecules interact with and organize the presynaptic and postsynaptic specializations of both excitatory and inhibitory central synapses. © The Authors (2010). Journal Compilation © Federation of European Neuroscience Societies and Blackwell Publishing Ltd.

UP-scaling of inverted small molecule based organic solar cells

DEFF Research Database (Denmark)

Patil, Bhushan Ramesh; Madsen, Morten

Organic solar cells (OSC), in spite of being a promising technology, still face challenges regarding large-scale fabrication. Although efficiencies of up to 12 % has been reached for small molecule OSC, their performance, both in terms of device efficiency and stability, is significantly reduced...... during up-scaling processes. The work presented here is focused on an approach towards up-scaling of small molecule based OSC with inverted device configuration. Bilayer OSC from Tetraphenyldibenzoperiflanthene (DBP) and Fullerenes (C70), as electron donor and acceptor respectively, with cell area...

Organic molecules based on dithienyl-2,1,3-benzothiadiazole as new donor materials for solution-processed organic photovoltaic cells

Energy Technology Data Exchange (ETDEWEB)

Wu, Zhonglian; Fan, Benhu; Ouyang, Jianyong [Department of Materials Science and Engineering, National University of Singapore, Singapore 117574 (Singapore); Xue, Feng [Department of Chemistry, National University of Singapore, Singapore 117573 (Singapore); Adachi, Chihaya [Center for Future Chemistry, Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395 (Japan)

2010-12-15

Polymers based on dithienyl-2,1,3-benzothiadiazole (TBT) have received strong attention as the donor materials of polymer photovoltaic cells (PVs), since they can have a low band gap. But soluble small organic molecules based on TBT have been rarely studied. This paper reports the synthesis of two small organic molecules based on TBT and their application as the donor materials of solution-processed bulk heterojunction organic photovoltaic cells (OPVs). These compounds were soluble in common organic solvents, such as chloroform, chlorobenzene and tetrahydrofuran. They have band gaps comparable to poly(3-hexylthiophene) (P3HT) and lower HOMO and LUMO (HOMO: highest occupied molecular orbital, LUMO: lowest unoccupied molecular orbital) levels than P3HT. These molecules and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) were used as the donors and acceptor to fabricate bulk heterojunction OPVs through solution processing. After optimization of the experimental conditions, power conversion efficiency (PCE) of 0.66% was achieved on the solution-processed OPVs under AM 1.5G, 100 mW cm{sup -2} illumination. (author)

Deterministic self-organization: Ordered positioning of InAs quantum dots by self-organized anisotropic strain engineering on patterned GaAs(311)B

International Nuclear Information System (INIS)

Selcuk, E.; Hamhuis, G.J.; Noetzel, R.

2009-01-01

Laterally ordered InGaAs quantum dot (QD) arrays, InAs QD molecules, and single InAs QDs in a spot-like periodic arrangement are created by self-organized anisotropic strain engineering of InGaAs/GaAs superlattice (SL) templates on planar GaAs (311)B substrates in molecular beam epitaxy. On shallow- and deep-patterned substrates the respectively generated steps and facets guide the self-organization process during SL template formation to create more complex ordering such as periodic stripes, depending on pattern design. Here we demonstrate for patterns such as shallow- and deepetched round holes and deep-etched zigzag mesas that the self-organized periodic arrangement of QD molecules and single QDs is spatially locked to the pattern sidewalls and corners. This extends the concept of guided self-organization to deterministic self-organization. Absolute position control of the QDs is achieved without one-to-one pattern definition. This guarantees the excellent arrangement control of the ordered QD molecules and single QDs with strong photoluminescence emission up to room temperature, which is required for future quantum functional devices. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Adsorption of polar organic molecules on sediments: Case-study on Callovian-Oxfordian claystone.

Science.gov (United States)

Rasamimanana, S; Lefèvre, G; Dagnelie, R V H

2017-08-01

The release and transport of anthropogenic organic matter through the geosphere is often an environmental criterion of safety. Sedimentary rocks are widely studied in this context as geological barriers for waste management. It is the case of Callovian-Oxfordian claystone (COx), for which several studies report adsorption of anthropogenic organic molecules. In this study, we evaluated and reviewed adsorption data of polar organic molecules on COx claystone. Experiments were performed on raw claystone, decarbonated and clay fractions. Adsorption isotherms were measured with adsorbates of various polarities: adipate, benzoate, ortho-phthalate, succinate, gluconate, oxalate, EDTA, citrate. A significant adsorption was observed for multidentate polycarboxylic acids as evidenced with phthalate, succinate, oxalate, gluconate, EDTA and citrate (R d  = 1.53, 3.52, 8.4, 8.8, 12.4, 54.7 L kg -1 respectively). Multiple linear regression were performed as a statistical analysis to determine the predictors from these adsorption data. A linear correlation between adsorption data (R d ) and dipole moment (μ) of adsorbates was evidenced (R 2  = 0.91). Molecules with a high dipole moment, μ(D) > 2.5, displayed a significant adsorption, R d ≫1 L kg -1 . A qualitative correlation can be easily estimated using the water/octanol partition coefficient, P ow , of adsorbates (R 2  = 0.77). In this case, two opposite trends were distinguished for polar and apolar molecules. The use of organic carbon content in sediments is relevant for predicting adsorption of apolar compounds, log (P ow )>+1. The oxides/clays contents may be relevant regarding polar molecules, log ( apparent P ow )<-1. The proposed scheme offers a general methodology for investigation of geo-barriers towards heterogeneous organic plumes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structural Design Principle of Small-Molecule Organic Semiconductors for Metal-Free, Visible-Light-Promoted Photocatalysis.

Science.gov (United States)

Wang, Lei; Huang, Wei; Li, Run; Gehrig, Dominik; Blom, Paul W M; Landfester, Katharina; Zhang, Kai A I

2016-08-08

Herein, we report on the structural design principle of small-molecule organic semiconductors as metal-free, pure organic and visible light-active photocatalysts. Two series of electron-donor and acceptor-type organic semiconductor molecules were synthesized to meet crucial requirements, such as 1) absorption range in the visible region, 2) sufficient photoredox potential, and 3) long lifetime of photogenerated excitons. The photocatalytic activity was demonstrated in the intermolecular C-H functionalization of electron-rich heteroaromates with malonate derivatives. A mechanistic study of the light-induced electron transport between the organic photocatalyst, substrate, and the sacrificial agent are described. With their tunable absorption range and defined energy-band structure, the small-molecule organic semiconductors could offer a new class of metal-free and visible light-active photocatalysts for chemical reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anchoring of organic molecules to a metal surface: HtBDC on Cu(110)

DEFF Research Database (Denmark)

Schunack, M.; Petersen, L.; Kuhnle, A.

2001-01-01

The interaction of largish molecules with metal surfaces has been studied by combining the imaging and manipulation capabilities of the scanning tunneling microscope (STM). At the atomic scale, the STM results directly reveal that the adsorption of a largish organic molecule can induce...

Organic Materials in the Undergraduate Laboratory: Microscale Synthesis and Investigation of a Donor-Acceptor Molecule

Science.gov (United States)

Pappenfus, Ted M.; Schliep, Karl B.; Dissanayake, Anudaththa; Ludden, Trevor; Nieto-Ortega, Belen; Lopez Navarrete, Juan T.; Ruiz Delgado, M. Carmen; Casado, Juan

2012-01-01

A series of experiments for undergraduate courses (e.g., organic, physical) have been developed in the area of small molecule organic materials. These experiments focus on understanding the electronic and redox properties of a donor-acceptor molecule that is prepared in a convenient one-step microscale reaction. The resulting intensely colored…

Organic hybrid planar-nanocrystalline bulk heterojunctions

Science.gov (United States)

Forrest, Stephen R [Ann Arbor, MI; Yang, Fan [Piscataway, NJ

2011-03-01

A photosensitive optoelectronic device having an improved hybrid planar bulk heterojunction includes a plurality of photoconductive materials disposed between the anode and the cathode. The photoconductive materials include a first continuous layer of donor material and a second continuous layer of acceptor material. A first network of donor material or materials extends from the first continuous layer toward the second continuous layer, providing continuous pathways for conduction of holes to the first continuous layer. A second network of acceptor material or materials extends from the second continuous layer toward the first continuous layer, providing continuous pathways for conduction of electrons to the second continuous layer. The first network and the second network are interlaced with each other. At least one other photoconductive material is interspersed between the interlaced networks. This other photoconductive material or materials has an absorption spectra different from the donor and acceptor materials.

Strategies for increasing the efficiency of heterojunction organic solar cells: material selection and device architecture.

Science.gov (United States)

Heremans, Paul; Cheyns, David; Rand, Barry P

2009-11-17

Thin-film blends or bilayers of donor- and acceptor-type organic semiconductors form the core of heterojunction organic photovoltaic cells. Researchers measure the quality of photovoltaic cells based on their power conversion efficiency, the ratio of the electrical power that can be generated versus the power of incident solar radiation. The efficiency of organic solar cells has increased steadily in the last decade, currently reaching up to 6%. Understanding and combating the various loss mechanisms that occur in processes from optical excitation to charge collection should lead to efficiencies on the order of 10% in the near future. In organic heterojunction solar cells, the generation of photocurrent is a cascade of four steps: generation of excitons (electrically neutral bound electron-hole pairs) by photon absorption, diffusion of excitons to the heterojunction, dissociation of the excitons into free charge carriers, and transport of these carriers to the contacts. In this Account, we review our recent contributions to the understanding of the mechanisms that govern these steps. Starting from archetype donor-acceptor systems of planar small-molecule heterojunctions and solution-processed bulk heterojunctions, we outline our search for alternative materials and device architectures. We show that non-planar phthalocynanines have appealing absorption characteristics but also have reduced charge carrier transport. As a result, the donor layer needs to be ultrathin, and all layers of the device have to be tuned to account for optical interference effects. Using these optimization techniques, we illustrate cells with 3.1% efficiency for the non-planar chloroboron subphthalocyanine donor. Molecules offering a better compromise between absorption and carrier mobility should allow for further improvements. We also propose a method for increasing the exciton diffusion length by converting singlet excitons into long-lived triplets. By doping a polymer with a

In-situ Evaluation of Soil Organic Molecules: Functional Group Chemistry Aggregate Structures, Metal and Surface Complexation Using Soft X-Ray

International Nuclear Information System (INIS)

Myneni, Satish C.

2008-01-01

Organic molecules are common in all Earth surface environments, and their composition and chemistry play an important role in a variety of biogeochemical reactions, such as mineral weathering, nutrient cycling and the solubility and transport of contaminants. However, most of what we know about the chemistry of these molecules comes from spectroscopy and microscopy studies of organic molecules extracted from different natural systems using either inorganic or organic solvents. Although all these methods gave us clues about the composition of these molecules, their composition and structure change with the extraction and the type of ex-situ analysis, their true behavior is less well understood. The goal of this project is to develop synchrotron instrumentation for studying natural organics, and to apply these recently developed synchrotron X-ray spectroscopy and microscopy techniques for understanding the: (1) functional group composition of naturally occurring organic molecules; (2) macromolecular structures of organic molecules; and (3) the nature of interactions of organic molecules with mineral surfaces in different environmental conditions.

Nanocoating of titanium implant surfaces with organic molecules. Polysaccharides including glycosaminoglycans

DEFF Research Database (Denmark)

Gurzawska, Katarzyna Aleksandra; Svava, Rikke; Jørgensen, Niklas Rye

2012-01-01

Long-term stability of titanium implants are dependent on a variety of factors. Nanocoating with organic molecules is one of the method used to improve osseointegration. Nanoscale modification of titanium implants affects surface properties, such as hydrophilicity, biochemical bonding capacity...... and roughness. This influences cell behaviour on the surface such as adhesion, proliferation and differentiation of cells as well as the mineralization of the extracellular matrix at the implant surfaces. The aim of the present systematic review was to describe organic molecules used for surface nanocoating...... nanocoatings. The included in vivo studies, showed improvement of bone interface reactions measured as increased Bone-to-Implant Contact length and Bone Mineral Density adjacent to the polysaccharide coated surfaces. Based on existing literature, surface modification with polysaccharide and glycosaminoglycans...

Biradical and triradical organic magnetic molecules as spin filters and rectifiers

International Nuclear Information System (INIS)

Zhu, L.; Yao, K.L.; Liu, Z.L.

2012-01-01

Graphical abstract: (a) Negative differential resistance (NDR) characteristic and antiparallel spin-current (ASC) rectification; (b) spin-current (SC) rectification and charge-current (CC) rectification properties Display Omitted Highlights: ► Organic magnetic molecules at gold electrodes as spin/charge rectifier. ► Spin diode/rectification stems from length and asymmetry of molecular framework. ► Negative differential resistance, spin-filtering and switching evidenced. - Abstract: We have theoretically investigated the spin-polarized transport properties of molecular junctions consisting of biradical and triradical organic magnetic molecules sandwiched between two symmetric gold electrodes, respectively. It shows that these junctions function as a spin rectifier or a combination of spin and charge rectifiers with high spin rectification ratios exceeding 100, wherein the spin diode/rectification effect stems from the conjugated length and asymmetry of the molecular framework, which is the pre-requisite for electronic asymmetry of the adsorbed species. The negative differential resistance, spin-filtering and switching properties are also unveiled. In particular, it is revealed that the strong couplings between the electrodes and molecules are responsible for the negative differential resistance.

Self-organized lattice of ordered quantum dot molecules

International Nuclear Information System (INIS)

Lippen, T. von; Noetzel, R.; Hamhuis, G.J.; Wolter, J.H.

2004-01-01

Ordered groups of InAs quantum dots (QDs), lateral QD molecules, are created by self-organized anisotropic strain engineering of a (In,Ga)As/GaAs superlattice (SL) template on GaAs (311)B in molecular-beam epitaxy. During stacking, the SL template self-organizes into a two-dimensionally ordered strain modulated network on a mesoscopic length scale. InAs QDs preferentially grow on top of the nodes of the network due to local strain recognition. The QDs form a lattice of separated groups of closely spaced ordered QDs whose number can be controlled by the GaAs separation layer thickness on top of the SL template. The QD groups exhibit excellent optical properties up to room temperature

Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing

KAUST Repository

Rancatore, Benjamin J.

2016-01-21

© 2016 American Chemical Society. Small molecules (SMs) with unique optical or electronic properties provide an opportunity to incorporate functionality into block copolymer (BCP)-based supramolecules. However, the assembly of supramolecules based on these highly crystalline molecules differs from their less crystalline counterparts. Here, two families of organic semiconductor SMs are investigated, where the composition of the crystalline core, the location (side- vs end-functionalization) of the alkyl solubilizing groups, and the constitution (branched vs linear) of the alkyl groups are varied. With these SMs, we present a systematic study of how the phase behavior of the SMs affects the overall assembly of these organic semiconductor-based supramolecules. The incorporation of SMs has a large effect on the interfacial curvature, the supramolecular periodicity, and the overall supramolecular morphology. The crystal packing of the SM within the supramolecule does not necessarily lead to the assembly of the comb block within the BCP microdomains, as is normally observed for alkyl-containing supramolecules. An unusual lamellar morphology with a wavy interface between the microdomains is observed due to changes in the packing structure of the small molecule within BCP microdomains. Since the supramolecular approach is modular and small molecules can be readily switched out, present studies provide useful guidance toward access supramolecular assemblies over several length scales using optically active and semiconducting small molecules.

Raman scattering in semiconductor structures based on monophthalocyanine and triphthalocyanine molecules incorporating erbium ions

International Nuclear Information System (INIS)

Belogorokhov, I. A.; Tikhonov, E. V.; Breusova, M. O.; Pushkarev, V. E.; Zoteev, A. V.; Tomilova, L. G.; Khokhlov, D. R.

2007-01-01

Semiconductor structures of the type of butyl-substituted erbium monophthalocyanine and triphthalocyanine are studied by Raman spectroscopy. It is shown that, when the sandwich-like structure of the molecule incorporating two complexing atoms between the ligands is considered instead of the planar molecular structure with one ligand and one metal atom, a series of lines appears in the Raman spectrum. In this series, the wave numbers of the lines represent an arithmetic progression with the arithmetical ratio ∼80 cm -1 . It is suggested that this feature is due to the larger number of organic molecules per metal atom in the triphthalocyanine complex, and the four Raman peaks at the frequencies 122, 208, 280, and 362 cm -1 are the manifestation of slight out-of-plane vibrations of the phthalocyanine ligands

EVAPORATION: a new vapour pressure estimation methodfor organic molecules including non-additivity and intramolecular interactions

Directory of Open Access Journals (Sweden)

S. Compernolle

2011-09-01

Full Text Available We present EVAPORATION (Estimation of VApour Pressure of ORganics, Accounting for Temperature, Intramolecular, and Non-additivity effects, a method to predict (subcooled liquid pure compound vapour pressure p⁰ of organic molecules that requires only molecular structure as input. The method is applicable to zero-, mono- and polyfunctional molecules. A simple formula to describe log₁₀p⁰(T is employed, that takes into account both a wide temperature dependence and the non-additivity of functional groups. In order to match the recent data on functionalised diacids an empirical modification to the method was introduced. Contributions due to carbon skeleton, functional groups, and intramolecular interaction between groups are included. Molecules typically originating from oxidation of biogenic molecules are within the scope of this method: aldehydes, ketones, alcohols, ethers, esters, nitrates, acids, peroxides, hydroperoxides, peroxy acyl nitrates and peracids. Therefore the method is especially suited to describe compounds forming secondary organic aerosol (SOA.

Molecular Packing and Arrangement Govern the Photo-Oxidative Stability of Organic Photovoltaic Materials

KAUST Repository

Mateker, William R.; Heumueller, Thomas; Cheacharoen, Rongrong; Sachs-Quintana, I. T.; Warnan, Julien; Liu, Xiaofeng; Bazan, Guillermo C.; Beaujuge, Pierre; McGehee, Michael D.

2015-01-01

For long-term performance chemically robust materials are desired for organic solar cells (OSCs). Illuminating neat films of OSC materials in air and tracking the rate of absorption loss, or photobleaching, can quickly screen a material’s photo-chemical stability. In this report, we photobleach neat films of OSC materials including polymers, solution-processed oligomers, solution-processed small molecules, and vacuum-deposited small molecules. Across the materials we test, we observe photobleaching rates that span seven orders of magnitude. Furthermore, we find that the film morphology of any particular material impacts the observed photobleaching rate, and that amorphous films photobleach faster than crystalline ones. In an extreme case, films of amorphous rubrene photobleach at a rate 2500 times faster than polycrystalline films. When we compare density to photobleaching rate, we find that stability increases with density. We also investigate the relationship between backbone planarity and chemical reactivity. The polymer PBDTTPD is more photostable than it’s more twisted and less ordered furan derivitative, PBDFTPD. Finally, we relate our work to what is known about the chemical stability of structural polymers, organic pigments, and organic light emitting diode materials. For the highest chemical stability, planar materials that form dense, crystalline film morphologies should be designed for OSCs.

Molecular Packing and Arrangement Govern the Photo-Oxidative Stability of Organic Photovoltaic Materials

KAUST Repository

Mateker, William R.

2015-08-19

For long-term performance chemically robust materials are desired for organic solar cells (OSCs). Illuminating neat films of OSC materials in air and tracking the rate of absorption loss, or photobleaching, can quickly screen a material’s photo-chemical stability. In this report, we photobleach neat films of OSC materials including polymers, solution-processed oligomers, solution-processed small molecules, and vacuum-deposited small molecules. Across the materials we test, we observe photobleaching rates that span seven orders of magnitude. Furthermore, we find that the film morphology of any particular material impacts the observed photobleaching rate, and that amorphous films photobleach faster than crystalline ones. In an extreme case, films of amorphous rubrene photobleach at a rate 2500 times faster than polycrystalline films. When we compare density to photobleaching rate, we find that stability increases with density. We also investigate the relationship between backbone planarity and chemical reactivity. The polymer PBDTTPD is more photostable than it’s more twisted and less ordered furan derivitative, PBDFTPD. Finally, we relate our work to what is known about the chemical stability of structural polymers, organic pigments, and organic light emitting diode materials. For the highest chemical stability, planar materials that form dense, crystalline film morphologies should be designed for OSCs.

Luminescence stability of porous Si terminated by hydrophilic organic molecules

Science.gov (United States)

Matsumoto, Kimihisa; Kamiguchi, Masao; Kamiya, Kazuhide; Nomura, Takashi; Suzuki, Shinya

2016-02-01

The effects of the surface termination of a porous Si surface by propionic acid and by undecylenic acid on their hydrophilicity and luminescence stability were studied. In the measurements of the contact angle of water droplets on porous Si films, the hydrophilicity of porous Si is improved by the surface termination each types of organic molecule. The PL intensity of as-prepared porous Si decreased with increasing aging time in ambient air. As PL quenching involves PL blue shift and increasing Si-O bonds density, nonradiative recombination centers are formed in the surface oxide. After the hydrosilylation process of propionic acid and undecylenic acid, PL intensity decreased and became 30% that of as-prepared porous Si film. However, the PL intensity was stable and exceeded that of the as-prepared film after 1000 min of aging in the ambient air. The PL stabilities are contributed to the termination by organic molecules that inhibits surface oxidation.

Organic molecule fluorescence as an experimental test-bed for quantum jumps in thermodynamics.

Science.gov (United States)

Browne, Cormac; Farrow, Tristan; Dahlsten, Oscar C O; Taylor, Robert A; Vlatko, Vedral

2017-08-01

We demonstrate with an experiment how molecules are a natural test bed for probing fundamental quantum thermodynamics. Single-molecule spectroscopy has undergone transformative change in the past decade with the advent of techniques permitting individual molecules to be distinguished and probed. We demonstrate that the quantum Jarzynski equality for heat is satisfied in this set-up by considering the time-resolved emission spectrum of organic molecules as arising from quantum jumps between states. This relates the heat dissipated into the environment to the free energy difference between the initial and final state. We demonstrate also how utilizing the quantum Jarzynski equality allows for the detection of energy shifts within a molecule, beyond the relative shift.

A-π-D-π-A Electron-Donating Small Molecules for Solution-Processed Organic Solar Cells: A Review.

Science.gov (United States)

Wang, Zhen; Zhu, Lingyun; Shuai, Zhigang; Wei, Zhixiang

2017-11-01

Organic solar cells based on semiconducting polymers and small molecules have attracted considerable attention in the last two decades. Moreover, the power conversion efficiencies for solution-processed solar cells containing A-π-D-π-A-type small molecules and fullerenes have reached 11%. However, the method for designing high-performance, photovoltaic small molecules still remains unclear. In this review, recent studies on A-π-D-π-A electron-donating small molecules for organic solar cells are introduced. Moreover, the relationships between molecular properties and device performances are summarized, from which inspiration for the future design of high performance organic solar cells may be obtained. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible multi-electron redox chemistry of π-conjugated N-containing heteroaromatic molecule-based organic cathodes

Science.gov (United States)

Peng, Chengxin; Ning, Guo-Hong; Su, Jie; Zhong, Guiming; Tang, Wei; Tian, Bingbing; Su, Chenliang; Yu, Dingyi; Zu, Lianhai; Yang, Jinhu; Ng, Man-Fai; Hu, Yong-Sheng; Yang, Yong; Armand, Michel; Loh, Kian Ping

2017-07-01

Even though organic molecules with well-designed functional groups can be programmed to have high electron density per unit mass, their poor electrical conductivity and low cycle stability limit their applications in batteries. Here we report a facile synthesis of π-conjugated quinoxaline-based heteroaromatic molecules (3Q) by condensation of cyclic carbonyl molecules with o-phenylenediamine. 3Q features a number of electron-deficient pyrazine sites, where multiple redox reactions take place. When hybridized with graphene and coupled with an ether-based electrolyte, an organic cathode based on 3Q molecules displays a discharge capacity of 395 mAh g-1 at 400 mA g-1 (1C) in the voltage range of 1.2-3.9 V and a nearly 70% capacity retention after 10,000 cycles at 8 A g-1. It also exhibits a capacity of 222 mAh g-1 at 20C, which corresponds to 60% of the initial specific capacity. Our results offer evidence that heteroaromatic molecules with multiple redox sites are promising in developing high-energy-density, long-cycle-life organic rechargeable batteries.

Mechanochemical synthesis of small organic molecules

Directory of Open Access Journals (Sweden)

Tapas Kumar Achar

2017-09-01

Full Text Available With the growing interest in renewable energy and global warming, it is important to minimize the usage of hazardous chemicals in both academic and industrial research, elimination of waste, and possibly recycle them to obtain better results in greener fashion. The studies under the area of mechanochemistry which cover the grinding chemistry to ball milling, sonication, etc. are certainly of interest to the researchers working on the development of green methodologies. In this review, a collection of examples on recent developments in organic bond formation reactions like carbon–carbon (C–C, carbon–nitrogen (C–N, carbon–oxygen (C–O, carbon–halogen (C–X, etc. is documented. Mechanochemical syntheses of heterocyclic rings, multicomponent reactions and organometallic molecules including their catalytic applications are also highlighted.

Conduction mechanism in assemblies of metal nanoparticles linked by organic molecules

International Nuclear Information System (INIS)

Mueller, K.-H.; Herrmann, J.; Raguse, B.; Baxter, G.; Reda, T.

2002-01-01

Full text: We have investigated theoretically and experimentally electron transport through thin films of gold nanoparticles which are linked by alkanedithiol molecules of different chain lengths. We find that conduction between neighbouring nanoparticles takes place by electron tunnelling along weakly conducting organic linker molecules. Using a tight binding model for the alkanedithiol molecules to describe the tunnelling process we predict the conductivity to decrease exponentially with the length of the molecules. During tunnelling the electron has to overcome a charging energy due to the electron-hole interaction between tunnelling electrons and the corresponding holes left behind on the donor nanoparticle. Experimentally we find that large applied voltages cause nonlinear I-V characteristics and that the temperature dependence of the conductivity does not show Arrhenius behaviour but instead is of the form exp[-(E o /kT) 1/2 ]. Using percolation theory for a network of metal nanoparticles separated by barriers we show that strong disorder caused by variations in nanoparticle size and linker length as well as randomly trapped electric charges on the linker molecules can well explain our experimental data

Biradical and triradical organic magnetic molecules as spin filters and rectifiers

Energy Technology Data Exchange (ETDEWEB)

Zhu, L. [School of Physics, School of Optoelectronics Science and Engineering, Wuhan Pulsed Magnetic Field Center, Huazhong University of Science and Technology, Wuhan 430074 (China); Yao, K.L., E-mail: klyao@hust.edu.cn [School of Physics, School of Optoelectronics Science and Engineering, Wuhan Pulsed Magnetic Field Center, Huazhong University of Science and Technology, Wuhan 430074 (China); International Center of Materials Physics, Chinese Academy of Science, Shengyang 110015 (China); Liu, Z.L. [School of Physics, School of Optoelectronics Science and Engineering, Wuhan Pulsed Magnetic Field Center, Huazhong University of Science and Technology, Wuhan 430074 (China)

2012-03-13

Graphical abstract: (a) Negative differential resistance (NDR) characteristic and antiparallel spin-current (ASC) rectification; (b) spin-current (SC) rectification and charge-current (CC) rectification properties Display Omitted Highlights: Black-Right-Pointing-Pointer Organic magnetic molecules at gold electrodes as spin/charge rectifier. Black-Right-Pointing-Pointer Spin diode/rectification stems from length and asymmetry of molecular framework. Black-Right-Pointing-Pointer Negative differential resistance, spin-filtering and switching evidenced. - Abstract: We have theoretically investigated the spin-polarized transport properties of molecular junctions consisting of biradical and triradical organic magnetic molecules sandwiched between two symmetric gold electrodes, respectively. It shows that these junctions function as a spin rectifier or a combination of spin and charge rectifiers with high spin rectification ratios exceeding 100, wherein the spin diode/rectification effect stems from the conjugated length and asymmetry of the molecular framework, which is the pre-requisite for electronic asymmetry of the adsorbed species. The negative differential resistance, spin-filtering and switching properties are also unveiled. In particular, it is revealed that the strong couplings between the electrodes and molecules are responsible for the negative differential resistance.

Phase-coherent electron transport through metallic atomic-sized contacts and organic molecules

Energy Technology Data Exchange (ETDEWEB)

Pauly, F.

2007-02-02

This work is concerned with the theoretical description of systems at the nanoscale, in particular the electric current through atomic-sized metallic contacts and organic molecules. In the first part, the characteristic peak structure in conductance histograms of different metals is analyzed within a tight-binding model. In the second part, an ab-initio method for quantum transport is developed and applied to single-atom and single-molecule contacts. (orig.)

Laser-induced desorption of organic molecules from front- and back-irradiated metal foils

International Nuclear Information System (INIS)

Zinovev, Alexander V.; Veryovkin, Igor V.; Pellin, Michael J.

2009-01-01

Laser-Induced Acoustic Desorption (LIAD) from thin metal foils is a promising technique for gentle and efficient volatilization of intact organic molecules from surfaces of solid substrates. Using the Single Photon Ionization (SPI) method combined with time-of-flight mass-spectrometry (TOF MS), desorbed flux in LIAD was examined and compared to that from direct laser desorption (LD). Molecules of various organic dyes were used in experiments. Translational velocities of the desorbed intact molecules did not depend on the desorbing laser intensity, which implies the presence of more sophisticated mechanism of energy transfer than the direct mechanical or thermal coupling between the laser pulse and the adsorbed molecules. The results of our experiments indicate that the LIAD phenomenon cannot be described in terms of a simple mechanical shake-off nor the direct laser desorption. Rather, they suggest that multi-step energy transfer processes are involved. Possible qualitative mechanism of LIAD that are based on formation of non-equilibrium energy states in the adsorbate-substrate system are proposed and discussed.

Comparative methods for quantifying thyroid volume using planar imaging and SPECT

International Nuclear Information System (INIS)

Zaidi, H.

1996-01-01

Thyroid volume determination using planar imaging is a procedure often performed in routine nuclear medicine, but is hampered by several physical difficulties, in particular by structures which overlie or underlie the organ of interest. SPECT enables improved accuracy over planar imaging in the determination of the volume since it is derived from the 3-D data rather than from a 2-D projection with a certain geometric assumption regarding the thyroid configuration. By using the phantoms of known volume, it was possible to estimate the accuracy of 3 different methods of determining thyroid volume from planar imaging used in clinical routine. The experimental results demonstrate that compared with conventional scintigraphy, thyroid phantom volumes were most accurately determined with SPECT when attenuation and scatter corrections are performed which allows accurate radiation dosimetry in humans without the need for assumptions on organ size or concentrations. Poster 181. (author)

Hydrogen transfer reactions of interstellar Complex Organic Molecules

Science.gov (United States)

Álvarez-Barcia, S.; Russ, P.; Kästner, J.; Lamberts, T.

2018-06-01

Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CHnO fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules. We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.

Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis

Science.gov (United States)

Francois, P.; Szopa, C.; Buch, A.; Coll, P.; McAdam, A. C.; Mahaffy, P. R.; Freissinet, C.; Glavin, D. P.; Navarro-Gonzalez, R.; Cabane, M.

2016-01-01

Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

The T-cell accessory molecule CD4 recognizes a monomorphic determinant on isolated Ia

DEFF Research Database (Denmark)

Gay, D; Buus, S; Pasternak, J

1988-01-01

The membrane protein CD4 is commonly found on mature T cells specific for antigen in association with class II major histocompatibility complex (MHC; Ia) proteins. This correlation has led to the suggestion that CD4 binds to a monomorphic region of the Ia molecule on the antigen-presenting cell...... proteins into a planar membrane system, we show that different Ia molecules can greatly enhance the ability of a CD4+ but not a CD4- variant of this class I-restricted T hybrid to respond to isolated class I molecules. T-cell responses can be strongly augmented by the concurrent expression of CD4 on the T...... cell and any of four different Ia proteins on planar membranes, thus supporting the idea that CD4 binds to a monomorphic region of the Ia molecule and increases the avidity with which the T cell can interact with its target....

Influence of thermocleavable functionality on organic field-effect transistor performance of small molecules

Science.gov (United States)

Mahale, Rajashree Y.; Dharmapurikar, Satej S.; Chini, Mrinmoy Kumar; Venugopalan, Vijay

2017-06-01

Diketopyrrolopyrrole based donor-acceptor-donor conjugated small molecules using ethylene dioxythiophene as a donor was synthesized. Electron deficient diketopyrrolopyrrole unit was substituted with thermocleavable (tert-butyl acetate) side chains. The thermal treatment of the molecules at 160 °C eliminated the tert-butyl ester group results in the formation of corresponding acid. Optical and theoretical studies revealed that the molecules adopted a change in molecular arrangement after thermolysis. The conjugated small molecules possessed p-channel charge transport characteristics in organic field effect transistors. The charge carrier mobility was increased after thermolysis of tert-butyl ester group to 5.07 × 10-5 cm2/V s.

Quantum transport through organic molecules

International Nuclear Information System (INIS)

Maiti, Santanu K.

2007-01-01

We investigate the electronic transport for the model of benzene-1, 4-dithiolate (BDT) molecule and some other geometric models of benzene molecule attached with two semi-infinite metallic electrodes by the use of Green's function technique. An analytic approach for the electronic transport through the molecular bridges is presented, based on the tight-binding model. Transport of electrons in such molecular bridges is strongly affected by the geometry of the molecules and their coupling strength with the electrodes. Conductance (g) shows resonance peaks associated with the molecular energy eigenstates. In the weak molecule-to-electrodes coupling limit current (I) passing through the molecules shows staircase-like behavior with sharp steps, while, it varies quite continuously in the limit of strong molecular coupling with the applied bias voltage (V). In presence of the transverse magnetic field conductance gives oscillatory behavior with flux φ, threaded by the molecular ring, showing φ 0 ( = ch/e) flux-quantum periodicity. Though conductance changes with the application of transverse magnetic field, but the current-voltage characteristics remain same in presence of this magnetic field for these molecular bridge systems

The effect of volume-of-interest misregistration on quantitative planar activity and dose estimation

International Nuclear Information System (INIS)

Song, N; Frey, E C; He, B

2010-01-01

In targeted radionuclide therapy (TRT), dose estimation is essential for treatment planning and tumor dose response studies. Dose estimates are typically based on a time series of whole-body conjugate view planar or SPECT scans of the patient acquired after administration of a planning dose. Quantifying the activity in the organs from these studies is an essential part of dose estimation. The quantitative planar (QPlanar) processing method involves accurate compensation for image degrading factors and correction for organ and background overlap via the combination of computational models of the image formation process and 3D volumes of interest defining the organs to be quantified. When the organ VOIs are accurately defined, the method intrinsically compensates for attenuation, scatter and partial volume effects, as well as overlap with other organs and the background. However, alignment between the 3D organ volume of interest (VOIs) used in QPlanar processing and the true organ projections in the planar images is required. The aim of this research was to study the effects of VOI misregistration on the accuracy and precision of organ activity estimates obtained using the QPlanar method. In this work, we modeled the degree of residual misregistration that would be expected after an automated registration procedure by randomly misaligning 3D SPECT/CT images, from which the VOI information was derived, and planar images. Mutual information-based image registration was used to align the realistic simulated 3D SPECT images with the 2D planar images. The residual image misregistration was used to simulate realistic levels of misregistration and allow investigation of the effects of misregistration on the accuracy and precision of the QPlanar method. We observed that accurate registration is especially important for small organs or ones with low activity concentrations compared to neighboring organs. In addition, residual misregistration gave rise to a loss of precision

Light-induced magnetoresistance in solution-processed planar hybrid devices measured under ambient conditions.

Science.gov (United States)

Banerjee, Sreetama; Bülz, Daniel; Reuter, Danny; Hiller, Karla; Zahn, Dietrich R T; Salvan, Georgeta

2017-01-01

We report light-induced negative organic magnetoresistance (OMAR) measured in ambient atmosphere in solution-processed 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) planar hybrid devices with two different device architectures. Hybrid electronic devices with trench-isolated electrodes (HED-TIE) having a channel length of ca. 100 nm fabricated in this work and, for comparison, commercially available pre-structured organic field-effect transistor (OFET) substrates with a channel length of 20 µm were used. The magnitude of the photocurrent as well as the magnetoresistance was found to be higher for the HED-TIE devices because of the much smaller channel length of these devices compared to the OFETs. We attribute the observed light-induced negative magnetoresistance in TIPS-pentacene to the presence of electron-hole pairs under illumination as the magnetoresistive effect scales with the photocurrent. The magnetoresistance effect was found to diminish over time under ambient conditions compared to a freshly prepared sample. We propose that the much faster degradation of the magnetoresistance effect as compared to the photocurrent was due to the incorporation of water molecules in the TIPS-pentacene film.

Permeability of uncharged organic molecules in reverse osmosis desalination membranes.

Science.gov (United States)

Dražević, Emil; Košutić, Krešimir; Svalina, Marin; Catalano, Jacopo

2017-06-01

Reverse osmosis (RO) membranes are primarily designed for removal of salts i.e. for desalination of brackish and seawater, but they have also found applications in removal of organic molecules. While it is clear that steric exclusion is the dominant removal mechanism, the fundamental explanation for how and why the separation occurs remains elusive. Until recently there was no strong microscopic evidences elucidating the structure of the active polyamide layers of RO membranes, and thus they have been conceived as "black boxes"; or as an array of straight capillaries with a distribution of radii; or as polymers with a small amount of polymer free domains. The knowledge of diffusion and sorption coefficients is a prerequisite for understanding the intrinsic permeability of any organic solute in any polymer. At the same time, it is technically challenging to accurately measure these two fundamental parameters in very thin (20-300 nm) water-swollen active layers. In this work we have measured partition and diffusion coefficients and RO permeabilities of ten organic solutes in water-swollen active layers of two types of RO membranes, low (SWC4+) and high flux (XLE). We deduced from our results and recent microscopic studies that the solute flux of organic molecules in polyamide layer of RO membranes occurs in two domains, dense polymer (the key barrier layer) and the water filled domains. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solution processable organic polymers and small molecules for bulk-heterojunction solar cells: A review

International Nuclear Information System (INIS)

Sharma, G. D.

2011-01-01

Solution processed bulk heterojunction (BHJ) organic solar cells (OSCs) have gained wide interest in past few years and are established as one of the leading next generation photovoltaic technologies for low cost power production. Power conversion efficiencies up to 6% and 6.5% have been reported in the literature for single layer and tandem solar cells, respectively using conjugated polymers. A recent record efficiency about 8.13% with active area of 1.13 cm 2 has been reported. However Solution processable small molecules have been widely applied for photovoltaic (PV) devices in recent years because they show strong absorption properties, and they can be easily purified and deposited onto flexible substrates at low cost. Introducing different donor and acceptor groups to construct donor--acceptor (D--A) structure small molecules has proved to be an efficient way to improve the properties of organic solar cells (OSCs). The power conversion efficiency about 4.4 % has been reported for OSCs based on the small molecules. This review deals with the recent progress of solution processable D--A structure small molecules and discusses the key factors affecting the properties of OSCs based on D--A structure small molecules: sunlight absorption, charge transport and the energy level of the molecules.

Organization of extracting molecules of the diamide type: link with the extracting properties?

International Nuclear Information System (INIS)

Meridiano, Y.

2009-02-01

The aim of these studies is to establish a link between the different organizations of diamide extractants (used in the DIAMEX process) and their extracting properties. The effects of the key parameters leading the liquid-liquid extraction (concentration of extractant, nature of solute, activity of the aqueous phase, nature of the diluent and temperature) are studied: 1) at the supramolecular scale, with the characterization of the extractant organizations by vapor-pressure osmometry (VPO) and small angle neutron and X-ray scattering (SANS/SAXS) experiments; 2) at the molecular scale, with the quantification of the extracted solutes (water, nitric acid, metal nitrate) and the determination of extracted complexes stoichiometries by electro-spray mass spectrometry (ESI-MS) experiments. The DMDOHEMA molecule acts as a classical surfactant and forms aggregates of the reverse micelle type. Taking into account the established supramolecular diagrams, a quantitative link between the extractants structures and their extracting properties has been brought to light. To model the europium nitrate extraction, two approaches have been developed: - an approach based on mass action laws. Extractions equilibria have been proposed taking into account the supramolecular speciation; - an innovative approach considering the extracted ions as adsorbed on a specific surface of the extractant molecule which depends on the extractant organization state. The ion extraction can be considered as a sum of isotherms corresponding to the different states of organization. This approach allows to compare the extraction efficiency of an extracting molecule as a function of its organization state. (author)

Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

Science.gov (United States)

Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

2015-04-13

Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent-molecule-mediated manipulation of crystalline grains for efficient planar binary lead and tin triiodide perovskite solar cells

Science.gov (United States)

Zhu, Leize; Yuh, Brian; Schoen, Stefan; Li, Xinpei; Aldighaithir, Mohammed; Richardson, Beau J.; Alamer, Ahmed; Yu, Qiuming

2016-03-01

Binary lead and tin perovskites offer the benefits of narrower band gaps for broader adsorption of solar spectrum and better charge transport for higher photocurrent density. Here, we report the growth of large, smooth crystalline grains of bianry lead and tin triiodide perovskite films via a two-step solution process with thermal plus solvent vapor-assisted thermal annealing. The crystalline SnxPb1-xI2 films formed in the first step served as the templates for the formation of crystalline CH3NH3SnxPb1-xI3 films during the second step interdiffusion of methylammonium iodide (MAI). Followed by dimethylsulfoxide (DMSO) vapor-assisted thermal annealing, small, faceted perovskite grains grew into large, smooth grains via the possible mechanism involving bond breaking and reforming mediated by DMSO solvent molecules. The absorption onset was extended to 950 and 1010 nm for the CH3NH3SnxPb1-xI3 perovskites with x = 0.1 and 0.25, respectively. The highest PCE of 10.25% was achieved from the planar perovskite solar cell with the CH3NH3Sn0.1Pb0.9I3 layer prepared via the thermal plus DMSO vapor-assisted thermal annealing. This research provides a way to control and manipulate film morphology, grain size, and especially the distribution of metal cations in binary metal perovskite layers, which opens an avenue to grow perovskite materials with desired properties to enhance device performance.Binary lead and tin perovskites offer the benefits of narrower band gaps for broader adsorption of solar spectrum and better charge transport for higher photocurrent density. Here, we report the growth of large, smooth crystalline grains of bianry lead and tin triiodide perovskite films via a two-step solution process with thermal plus solvent vapor-assisted thermal annealing. The crystalline SnxPb1-xI2 films formed in the first step served as the templates for the formation of crystalline CH3NH3SnxPb1-xI3 films during the second step interdiffusion of methylammonium iodide (MAI

The tritium labelling of organic molecules by heterogeneous catalytic exchange

International Nuclear Information System (INIS)

Angoso, M.; Kaiser, F.

1977-01-01

The influence of the temperature at 65degC and 120degC on the labelling of three organic molecules with tritium was studied. The compounds were: benzoic acid, diphenyl glioxal and 2,3-tetramethylene-4-phenylthien-7-oxodiacetin. The method employed was the heterogeneous catalytic exchange between tritiaded water and the organic compound. The purification was made by thin-layer chromatography and the concentration, purity and specific activity of the products were determined by counting and ultraviolet techniques. The thermal stability and the radiolitic effects on labelled benzoic acid were also considered. (author) [es

Organic-Inorganic Hybrid Interfacial Layer for High-Performance Planar Perovskite Solar Cells.

Science.gov (United States)

Yang, Hao; Cong, Shan; Lou, Yanhui; Han, Liang; Zhao, Jie; Sun, Yinghui; Zou, Guifu

2017-09-20

4,7-Diphenyl-1,10-phenanthroline (Bphen) is an efficient electron transport and hole blocking material in organic photoelectric devices. Here, we report cesium carbonate (Cs 2 CO 3 ) doped Bphen as cathode interfacial layer in CH 3 NH 3 PbI 3-x Cl x based planar perovskite solar cells (PSCs). Investigation finds that introducing Cs 2 CO 3 suppresses the crystallization of Bphen and benefits a smooth interface contact between the perovskite and electrode, resulting in the decrease in carrier recombination and the perovskite degradation. In addition, the matching energy level of Bphen film in the PSCs effectively blocks the holes diffusion to cathode. The resultant power conversion efficiency (PCE) achieves as high as 17.03% in comparison with 12.67% of reference device without doping. Besides, experiments also demonstrate the stability of PSCs have large improvement because the suppressed crystallization of Bphen by doping Cs 2 CO 3 as a superior barrier layer blocks the Ag atom and surrounding moisture access to the vulnerable perovskite layer.

Access to Optically Pure β-Hydroxy Esters via Non-Enzymatic Kinetic Resolution by a Planar-Chiral DMAP Catalyst

Directory of Open Access Journals (Sweden)

Alba E. Díazlvarez

2014-09-01

Full Text Available The development of new approaches to obtain optically pure β-hydroxy esters is an important area in synthetic organic chemistry since they are precursors of other high value compounds. Herein, the kinetic resolution of racemic β-hydroxy esters using a planar-chiral DMAP derivative catalyst is presented. Following this procedure, a range of aromatic β-hydroxy esters was obtained in excellent selectivities (up to s = 107 and high enantiomeric excess (up to 99% ee. Furthermore, the utility of the present method was demonstrated in the synthesis of (S-3-hydroxy-N-methyl-3-phenylpropanamide, a key intermediate for bioactive molecules such as fluoxetine, tomoxetine or nisoxetine, in its enantiomerically pure form.

Application of the bootstrap method to radiolabeled antibody dosimetry from planar images

International Nuclear Information System (INIS)

Papenfuss, T.; Saunder, T.H.; Schleyer, P.J.; O'Keefe, G.J.; Scott, A.M.

2002-01-01

Full text: Planar imaging dosimetry of radiolabeled antibody treatment uses the MIRD schema to compute dose to an organ from the calculated activity in that and other organs. The calculated activity in an organ is a function of the average count rates in the organ, a standard and an appropriate background measurement. The geometric mean of conjugate averages, together with an attenuation factor is used to provide an approximate attenuation correction. It is sometimes desirable to know the variance of the activity in an organ in order to apply weighted least squares regression to the data. This is particularly important when incorporating more accurate data from autoradiography of biopsied tissue into the analysis, but is also useful when some data points have low signal. While the geometric mean image can be used to calculate the variance of an organ's count rate. It is difficult to calculate the variance of the activity, since the organ in question, the standard and the background all contribute to it. Bootstrap methods are Monte Carlo techniques that can be used to estimate parameters from data and to determine the accuracy of the estimation. By bootstrapping pixel values in the organ, background and standard ROIs, it is possible to calculate many realisations of the organ activity and calculate its variance. As an example, bootstrapping is applied to the pharmacodynamic analysis of 131 I-huA33 in colon. The data includes planar whole body images, and autoradiographs and planar images of a resected colon. Copyright (2002) The Australian and New Zealand Society of Nuclear Medicine Inc

Structural Dependence of Electronic Properties in A-A-D-A-A-Type Organic Solar Cell Material

Directory of Open Access Journals (Sweden)

Ram S. Bhatta

2015-01-01

Full Text Available Small conjugated molecules (SCMs are promising candidates for organic photovoltaic (OPV devices because of their structural simplicity, well control over synthetic reproducibility, and low purification cost. However, industrial development of SCM-based OPV devices requires improving their performance, which in turn relies on the fundamental understanding of structural dependence of electronic properties of SCMs. Herein, we report the structural and electronic properties of the BCNDTS molecule as a model system for acceptor-acceptor-donor-acceptor-acceptor (A-A-D-A-A type SCMs, using density functional theory (DFT and time-dependent DFT methods. Systematic calculations of two-dimensional potential energy surfaces, molecular electrostatic potential surfaces, ground state frontier molecular orbital energies, and the vertical excitation energies are performed. We found that the lowest energy conformation of the BCNDTS molecule is planar. The planar conformation favors the lowest ground state and the excited state energies as well as the strongest oscillator strength. The present results suggest that SCMs containing central dithienosilole cores connected with 2,1,3-benzothiadiazole groups have potential to be an efficient electron donor for OPV devices.

Doping effect on photoabsorption and charge-separation dynamics in light-harvesting organic molecule

Directory of Open Access Journals (Sweden)

Satoshi Ohmura

2016-01-01

Full Text Available Using ab-initio theoretical methods, we demonstrate possible enhancement of photo-conversion efficiency of an organic solar cell via intentional doping in molecular graphene-fullerene heterojunction [the hexabenzocoronene (HBC-triethylene glycol (TEG–C60 molecule]. Photoabsorption analysis indicates oxygen substitution into HBC leads to an extension of the spectra up to an infrared regime. A quantum-mechanical molecular dynamics simulation incorporating nonadiabatic electronic transitions reveals that a dissociated charge state (D+ and A- in the O-doped system is more stable than the pristine case due to the presence of an effective barrier by the TEG HOMO/LUMO level. We also find that oxygen doping in HBC enhances the intermolecular carrier mobility after charge separation. On the other hand, the pristine molecule undergoes rapid recombination between donor and acceptor charges at the interface. These analyses suggest that the graphene oxidation opens a new window in the application of organic super-molecules to solar cells.

Doping effect on photoabsorption and charge-separation dynamics in light-harvesting organic molecule

Energy Technology Data Exchange (ETDEWEB)

Ohmura, Satoshi, E-mail: s.ohmura.m4@cc.it-hiroshima.ac.jp [Research Center for Condensed Matter Physics, Department of Civil Engineering and Urban Design, Hiroshima Institute of Technology, Hiroshima 731-5193 (Japan); Tsuruta, Kenji [Department of Electrical and Electronic Engineering, Okayama University, Okayama 700-8530 (Japan); Shimojo, Fuyuki [Department of Physics, Kumamoto University, Kumamoto 860-8555 Japan (Japan); Nakano, Aiichiro [Collaboratory for Advanced Computing and Simulations, Department of Computer Science, Department of Physics & Astronomy, Department of Chemical Engineering & Materials Science, Department of Biological Sciences, University of Southern California, CA90089-024 (United States)

2016-01-15

Using ab-initio theoretical methods, we demonstrate possible enhancement of photo-conversion efficiency of an organic solar cell via intentional doping in molecular graphene-fullerene heterojunction [the hexabenzocoronene (HBC)-triethylene glycol (TEG)–C{sub 60} molecule]. Photoabsorption analysis indicates oxygen substitution into HBC leads to an extension of the spectra up to an infrared regime. A quantum-mechanical molecular dynamics simulation incorporating nonadiabatic electronic transitions reveals that a dissociated charge state (D{sup +} and A{sup -}) in the O-doped system is more stable than the pristine case due to the presence of an effective barrier by the TEG HOMO/LUMO level. We also find that oxygen doping in HBC enhances the intermolecular carrier mobility after charge separation. On the other hand, the pristine molecule undergoes rapid recombination between donor and acceptor charges at the interface. These analyses suggest that the graphene oxidation opens a new window in the application of organic super-molecules to solar cells.

Importance of dewetting in organic molecular-beam deposition: Pentacene on gold

International Nuclear Information System (INIS)

Beernink, G.; Strunskus, T.; Witte, G.; Woell, Ch.

2004-01-01

Organic molecular-beam deposition of pentacene on gold substrates has been investigated using a multitechnique approach. The morphology of the organic thin films depends strongly on the substrate temperature. Pronounced dewetting and island formation are observed at room temperature. Whereas pentacene molecules adopt a planar monolayer structure, they continue to grow in an upright orientation in multilayer films as inferred from x-ray absorption spectroscopy and atomic force microscopy. These results are in pronounced contrast to a recent scanning tunneling microscopy (STM) study by Kang and Zhu [Appl. Phys. Lett. 82, 3248 (2003)] and indicate fundamental problems in the interpretation of STM measurements for organic thin films

Organic Semiconductor-Containing Supramolecules: Effect of Small Molecule Crystallization and Molecular Packing

KAUST Repository

Rancatore, Benjamin J.; Kim, BongSoo; Mauldin, Clayton E.; Frechet, Jean; Xu, Ting

2016-01-01

on these highly crystalline molecules differs from their less crystalline counterparts. Here, two families of organic semiconductor SMs are investigated, where the composition of the crystalline core, the location (side- vs end-functionalization) of the alkyl

The tritium labelling of organic molecules by heterogeneous catalytic exchange

International Nuclear Information System (INIS)

Angoso Marina, M.; Kaiser Ruiz del Olmo, F.

1977-01-01

The influence of the temperature at 65 degree centigree and 120 degree centigree on the labelling of three organic molecules with tritium was studied. The compounds were: benzoic acid, de phenyl glyoxal and 2,3-tetramethylene-4-pantothenyl-7-oxo diacetin.The method employed was the heterogeneous catalytic exchange between tritiated water and the organic compound. The purification was made by thin-layer chromatography and the concentration, purity and specific activity of the products were determined by counting and ultraviolet techniques. The thermal stability and the radiolytic effects on labelled benzoic acid were also considered. (Author) 9 refs

Engineering a light-emitting planar defect within three-dimensional photonic crystals

Directory of Open Access Journals (Sweden)

Guiqiang Liu, Yan Chen and Zhiqing Ye

2009-01-01

Full Text Available Sandwich structures, constructed from a planar defect of rhodamine-B (RhB-doped titania (TiO2 and two photonic crystals, were synthesized via the self-assembly method combined with spin-coating. The modification of the spontaneous emission of RhB molecules in such structures was investigated experimentally. The spontaneous emission of RhB-doped TiO2 film with photonic crystals was reduced by a factor of 5.5 over a large bandwidth of 13% of the first-order Bragg diffraction frequency when compared with that of RhB-doped TiO2 film without photonic crystals. The angular dependence of the modification and the photoluminescence lifetime of RhB molecules demonstrate that the strong and wide suppression of the spontaneous emission of the RhB molecules is due to the presence of the photonic band gap.

Engineering a light-emitting planar defect within three-dimensional photonic crystals

Science.gov (United States)

Liu, Guiqiang; Chen, Yan; Ye, Zhiqing

2009-01-01

Sandwich structures, constructed from a planar defect of rhodamine-B (RhB)-doped titania (TiO2) and two photonic crystals, were synthesized via the self-assembly method combined with spin-coating. The modification of the spontaneous emission of RhB molecules in such structures was investigated experimentally. The spontaneous emission of RhB-doped TiO2 film with photonic crystals was reduced by a factor of 5.5 over a large bandwidth of 13% of the first-order Bragg diffraction frequency when compared with that of RhB-doped TiO2 film without photonic crystals. The angular dependence of the modification and the photoluminescence lifetime of RhB molecules demonstrate that the strong and wide suppression of the spontaneous emission of the RhB molecules is due to the presence of the photonic band gap. PMID:27877309

Development of new methods in modern selective organic synthesis: preparation of functionalized molecules with atomic precision

International Nuclear Information System (INIS)

Ananikov, V P; Khemchyan, L L; Ivanova, Yu V; Dilman, A D; Levin, V V; Bukhtiyarov, V I; Sorokin, A M; Prosvirin, I P; Romanenko, A V; Simonov, P A; Vatsadze, S Z; Medved'ko, A V; Nuriev, V N; Nenajdenko, V G; Shmatova, O I; Muzalevskiy, V M; Koptyug, I V; Kovtunov, K V; Zhivonitko, V V; Likholobov, V A

2014-01-01

The challenges of the modern society and the growing demand of high-technology sectors of industrial production bring about a new phase in the development of organic synthesis. A cutting edge of modern synthetic methods is introduction of functional groups and more complex structural units into organic molecules with unprecedented control over the course of chemical transformation. Analysis of the state-of-the-art achievements in selective organic synthesis indicates the appearance of a new trend — the synthesis of organic molecules, biologically active compounds, pharmaceutical substances and smart materials with absolute selectivity. Most advanced approaches to organic synthesis anticipated in the near future can be defined as 'atomic precision' in chemical reactions. The present review considers selective methods of organic synthesis suitable for transformation of complex functionalized molecules under mild conditions. Selected key trends in the modern organic synthesis are considered including the preparation of organofluorine compounds, catalytic cross-coupling and oxidative cross-coupling reactions, atom-economic addition reactions, methathesis processes, oxidation and reduction reactions, synthesis of heterocyclic compounds, design of new homogeneous and heterogeneous catalytic systems, application of photocatalysis, scaling up synthetic procedures to industrial level and development of new approaches to investigation of mechanisms of catalytic reactions. The bibliography includes 840 references

The Planar Sandwich and Other 1D Planar Heat Flow Test Problems in ExactPack

Energy Technology Data Exchange (ETDEWEB)

Singleton, Jr., Robert [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-01-24

This report documents the implementation of several related 1D heat flow problems in the verification package ExactPack [1]. In particular, the planar sandwich class defined in Ref. [2], as well as the classes PlanarSandwichHot, PlanarSandwichHalf, and other generalizations of the planar sandwich problem, are defined and documented here. A rather general treatment of 1D heat flow is presented, whose main results have been implemented in the class Rod1D. All planar sandwich classes are derived from the parent class Rod1D.

Intercalation of organic molecules into SnS2 single crystals

International Nuclear Information System (INIS)

Toh, M.L.; Tan, K.J.; Wei, F.X.; Zhang, K.K.; Jiang, H.; Kloc, C.

2013-01-01

SnS 2 is a layered semiconductor with a van der Waals gap separating the covalently bonded layers. In this study, post-synthesis intercalation of donor organic amine molecules, such as ethylenediamine (en), into tin disulfide and secondary intercalation of p-phenylenediamine (PPD) and 1, 5-naphthalenediamine (NDA) into SnS 2e n have been verified with X-ray diffraction. PPD and NDA did not intercalate directly even during prolonged annealing but replaced en readily if en was already present in the van der Waals gap. The c-lattice dilation is proportional to the intercalant size. Unit cell lattices of intercalated products were determined from the positions of the X-ray diffraction peaks. Optical images taken during the intercalation showed that intercalation progressed from the periphery towards the interior of the crystal. TEM diffraction patterns in the [0 0 1] direction of SnS 2 after intercalation revealed defects and stacking mismatches among the SnS 2 layers caused by the intercalation. UV–Vis absorption studies showed a red shift in the band edge of the SnS 2 material after intercalation. The band edge was 2.2 eV for pristine SnS 2 ; after intercalation with en or PPD, the absorbance spectra band edges shifted to approximately 0.7 eV or 0.5 eV, respectively. - Graphical Abstract: SnS 2 single crystals were intercalated with organic amine molecules such as ethylenediamine, phenylenediamine and naphthalenediamine. Absorption studies showed red shift of band edge after intercalation, which was consistent with optical observations. X-ray diffraction indicated lattice dilation in the c-lattice of SnS 2 after intercalation. Highlights: ► Organic molecules intercalated inhomogenously between covalently bonded SnS 2 layers. ► Ethylenediamine (en) intercalate directly into SnS 2 . ► Phenylenediamine (PPD) and naphthalenediamine (NDA) can be intercalated into SnS 2 secondary. ► In a secondary intercalation the bonds between layers are weakened by direct

Proposal of limit moment equation applicable to planar/non-planar flaw in wall thinned pipes under bending

International Nuclear Information System (INIS)

Tsuji, Masataka; Meshii, Toshiyuki

2011-01-01

Highlights: → A limit moment equation applicable to planar/non-planar flaw of 0 ≤ θ ≤ π found in wall thinned straight pipes was proposed. → An idea to rationally classify planar/non-planar flaw in wall thinned pipes was proposed. → The equation based on the experimental observation focused on the fracture mode. - Abstract: In this paper, a limit bending moment equation applicable to all types of planar and non-planar flaws in wall-thinned straight pipes under bending was proposed. A system to rationally classify the planar/non-planar flaws in wall-thinned pipes was suggested based on experimental observations focused on the fracture mode. The results demonstrate the importance of distinguishing between axial and circumferential long flaws in wall-thinned pipes.

Density Functional Investigation of Graphene Doped with Amine-Based Organic Molecules

Directory of Open Access Journals (Sweden)

Yeun Hee Hwang

2015-01-01

Full Text Available To improve the electronic properties of graphene, many doping techniques have been studied. Herein, we investigate the electronic and molecular structure of doped graphene using density functional theory, and we report the effects of amine-based benzene dopants adsorbed on graphene. Density functional theory (DFT calculations were performed to determine the role of amine-based aromatic compounds in graphene doping. These organic molecules bind to graphene through long-range interactions such as π-π interactions and C-H⋯π hydrogen bonding. We compared the electronic structures of pristine graphene and doped graphene to understand the electronic structure of doped graphene at the molecular level. Also, work functions of doped graphene were obtained from electrostatic potential calculations. A decrease in the work function was observed when the amine-based organic compounds were adsorbed onto graphene. Because these systems are based on physisorption, there was no obvious band structure change at point K at the Fermi level after doping. However, the amine-based organic dopants did change the absolute Fermi energy levels. In this study, we showed that the Fermi levels of the doped graphene were affected by the HOMO energy level of the dopants and by the intermolecular charge transfer between the adsorbed molecules and graphene.

Study of flowability effect on self-planarization performance at SOC materials

Science.gov (United States)

Yun, Huichan; Kim, Jinhyung; Park, Youjung; Kim, Yoona; Jeong, Seulgi; Baek, Jaeyeol; Yoon, Byeri; Lim, Sanghak

2017-03-01

For multilayer process, importance of carbon-based spin-on hardmask material that replaces amorphous carbon layer (ACL) is ever increasing. Carbon-based spin-on hardmask is an organic polymer with high carbon content formulated in organic solvents for spin-coating application that is cured through baking. In comparison to CVD process for ACL, carbon-based spin-on hardmask material can offer several benefits: lower cost of ownership (CoO) and improved process time, as well as better gap-fill and planarization performances. Thus carbon-based spin-on hardmask material of high etch resistance, good gap-fill properties and global planarization performances over various pattern topographies are desired to achieve the fine patterning and high aspect ratio (A/R). In particular, good level of global planarization of spin coated layer over the underlying pattern topographies is important for self-aligned double patterning (SADP) process as it dictates the photolithographic margin. Herein, we report a copolymer carbon-based spin-on hardmask resin formulation that exhibits favorable film shrinkage profile and good etch resistance properties. By combining the favorable characteristics of each resin - one resin with good shrinkage property and the other with excellent etch resistance into the copolymer, it was possible to achieve a carbonbased spin-on hardmask formulation with desirable level of etch resistance and the planarization performances across various underlying substrate pattern topographies.

Theory of photoelectron spectroscopy for organic molecules and their crystals

International Nuclear Information System (INIS)

Fujikawa, Takashi; Niki, Kaori; Sakuma, Hiroto

2015-01-01

Highlights: • Some specific features in photoemission theory from organic solids are reviewed. • Extrinsic and intrinsic effects are discussed. • Photoemission from extended levels is compared with that from core levels. • First principle many-body theories are discussed on the basis of nonequilibrium Green's functions. - Abstract: In this short review we discuss recent progress in photoemission theory for organic molecules and their crystals. We discuss some important features in Keldysh Green's function theory for the photoemission. We briefly discuss many-body aspects in photoemission from core and extended levels. In particular phonon effects are investigated in more detail since organic solids are typically soft where electron–phonon interaction is important. Debye–Waller factor suppresses the interference effects of photoelectron waves which makes ARPES analyses useless, particularly in high energy region.

Nucleation of Organic Molecules via a Hot Precursor State: Pentacene on Amorphous Mica

Science.gov (United States)

2013-01-01

Organic thin films have attracted considerable interest due to their applicability in organic electronics. The classical scenario for thin film nucleation is the diffusion-limited aggregation (DLA). Recently, it has been shown that organic thin film growth is better described by attachment-limited aggregation (ALA). However, in both cases, an unusual relationship between the island density and the substrate temperature was observed. Here, we present an aggregation model that goes beyond the classical DLA or ALA models to explain this behavior. We propose that the (hot) molecules impinging on the surface cannot immediately equilibrate to the substrate temperature but remain in a hot precursor state. In this state, the molecules can migrate considerable distances before attaching to a stable or unstable island. This results in a significantly smaller island density than expected by assuming fast equilibration and random diffusion. We have applied our model to pentacene film growth on amorphous Muscovite mica. PMID:24340130

Adsorption of organic molecules on mineral surfaces studied by first-principle calculations: A review.

Science.gov (United States)

Zhao, Hongxia; Yang, Yong; Shu, Xin; Wang, Yanwei; Ran, Qianping

2018-04-09

First-principle calculations, especially by the density functional theory (DFT) methods, are becoming a power technique to study molecular structure and properties of organic/inorganic interfaces. This review introduces some recent examples on the study of adsorption models of organic molecules or oligomers on mineral surfaces and interfacial properties obtained from first-principles calculations. The aim of this contribution is to inspire scientists to benefit from first-principle calculations and to apply the similar strategies when studying and tailoring interfacial properties at the atomistic scale, especially for those interested in the design and development of new molecules and new products. Copyright © 2017. Published by Elsevier B.V.

Molecular crowding of collagen: a pathway to produce highly-organized collagenous structures.

Science.gov (United States)

Saeidi, Nima; Karmelek, Kathryn P; Paten, Jeffrey A; Zareian, Ramin; DiMasi, Elaine; Ruberti, Jeffrey W

2012-10-01

Collagen in vertebrate animals is often arranged in alternating lamellae or in bundles of aligned fibrils which are designed to withstand in vivo mechanical loads. The formation of these organized structures is thought to result from a complex, large-area integration of individual cell motion and locally-controlled synthesis of fibrillar arrays via cell-surface fibripositors (direct matrix printing). The difficulty of reproducing such a process in vitro has prevented tissue engineers from constructing clinically useful load-bearing connective tissue directly from collagen. However, we and others have taken the view that long-range organizational information is potentially encoded into the structure of the collagen molecule itself, allowing the control of fibril organization to extend far from cell (or bounding) surfaces. We here demonstrate a simple, fast, cell-free method capable of producing highly-organized, anistropic collagen fibrillar lamellae de novo which persist over relatively long-distances (tens to hundreds of microns). Our approach to nanoscale organizational control takes advantage of the intrinsic physiochemical properties of collagen molecules by inducing collagen association through molecular crowding and geometric confinement. To mimic biological tissues which comprise planar, aligned collagen lamellae (e.g. cornea, lamellar bone or annulus fibrosus), type I collagen was confined to a thin, planar geometry, concentrated through molecular crowding and polymerized. The resulting fibrillar lamellae show a striking resemblance to native load-bearing lamellae in that the fibrils are small, generally aligned in the plane of the confining space and change direction en masse throughout the thickness of the construct. The process of organizational control is consistent with embryonic development where the bounded planar cell sheets produced by fibroblasts suggest a similar confinement/concentration strategy. Such a simple approach to nanoscale

A Nonfullerene Small Molecule Acceptor with 3D Interlocking Geometry Enabling Efficient Organic Solar Cells.

Science.gov (United States)

Lee, Jaewon; Singh, Ranbir; Sin, Dong Hun; Kim, Heung Gyu; Song, Kyu Chan; Cho, Kilwon

2016-01-06

A new 3D nonfullerene small-molecule acceptor is reported. The 3D interlocking geometry of the small-molecule acceptor enables uniform molecular conformation and strong intermolecular connectivity, facilitating favorable nanoscale phase separation and electron charge transfer. By employing both a novel polymer donor and a nonfullerene small-molecule acceptor in the solution-processed organic solar cells, a high-power conversion efficiency of close to 6% is demonstrated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adiabatic Field-Free Alignment of Asymmetric Top Molecules with an Optical Centrifuge.

Science.gov (United States)

Korobenko, A; Milner, V

2016-05-06

We use an optical centrifuge to align asymmetric top SO_{2} molecules by adiabatically spinning their most polarizable O-O axis. The effective centrifugal potential in the rotating frame confines the sulfur atoms to the plane of the laser-induced rotation, leading to the planar molecular alignment that persists after the molecules are released from the centrifuge. The periodic appearance of the full three-dimensional alignment, typically observed only with linear and symmetric top molecules, is also detected. Together with strong in-plane centrifugal forces, which bend the molecules by up to 10 deg, permanent field-free alignment offers new ways of controlling molecules with laser light.

Complex organic molecules in the Galactic Centre: the N-bearing family

Science.gov (United States)

Zeng, S.; Jiménez-Serra, I.; Rivilla, V. M.; Martín, S.; Martín-Pintado, J.; Requena-Torres, M. A.; Armijos-Abendaño, J.; Riquelme, D.; Aladro, R.

2018-05-01

We present an unbiased spectral line survey toward the Galactic Centre (GC) quiescent giant molecular cloud (QGMC), G+0.693 using the GBT and IRAM 30 telescopes. Our study highlights an extremely rich organic inventory of abundant amounts of nitrogen (N)-bearing species in a source without signatures of star formation. We report the detection of 17 N-bearing species in this source, of which 8 are complex organic molecules (COMs). A comparison of the derived abundances relative to H2 is made across various galactic and extragalactic environments. We conclude that the unique chemistry in this source is likely to be dominated by low-velocity shocks with X-rays/cosmic rays also playing an important role in the chemistry. Like previous findings obtained for O-bearing molecules, our results for N-bearing species suggest a more efficient hydrogenation of these species on dust grains in G+0.693 than in hot cores in the Galactic disk, as a consequence of the low dust temperatures coupled with energetic processing by X-ray/cosmic ray radiation in the GC.

Variability in DMSA reporting following urinary tract infection in children: pinhole, planar, and pinhole with planar

International Nuclear Information System (INIS)

Rossleigh, M.A.; Christian, C.L.; Craig, J.C.; Howman-Giles, R.B.; Grunewald, S.

2004-01-01

Purpose: To determine whether the provision of DMSA images obtained by pinhole collimation reduces inter-observer variability of reporting compared with planar DMSA images alone. Methods: One hundred consecutive DMSA images were independently interpreted three times (pinhole alone, planar alone, pinhole and planar) by four participating nuclear medicine specialists from different departments and in random order. The presence or absence of renal parenchymal abnormality was classified using the modified four level grading system of Goldraich with mean values for the 6 comparisons reported. Results: The proportion of DMSA images interpreted as abnormal was 31% for planar, 34% for pinhole and 33% for planar with pinhole. Agreement was 89% for planar alone, 89% for pinhole alone and 90% for planar with pinhole, with kappa values 0.74, 0.75 and 0.80 respectively for the normal-abnormal scan classification of individual children. These results did not vary appreciably whether interpretation of patients, kidneys or kidney zones was compared. Reasons for disagreement in reporting included different interpretations of 'abnormalities' as normal anatomical variations (splenic impression, fetal lobulation, duplex collecting systems, column of Bertin) or true parenchymal abnormalities, different adjustments in thresholds for reporting abnormality when images were technically suboptimal, different weighting given to pinhole and planar images when both were provided, and error. Conclusion: Four experienced nuclear medicine physicians showed substantial agreement in the interpretation of planar alone, pinhole alone and planar with pinhole DMSA images, but the provision of both sets of images, planar and pinhole, did not reduce variability. (authors)

Light incoupling in small molecule organic solar cells

Energy Technology Data Exchange (ETDEWEB)

Allinger, Nikola; Meiss, Jan; Riede, Moritz; Leo, Karl [Institut fuer Angewandte Photophysik, Technische Universitaet Dresden, 01069 Dresden (Germany); Gnehr, Wolf-Michael [Heliatek GmbH, Liebigstrasse 26, 01187 Dresden (Germany)

2008-07-01

Light incoupling is an essential topic for optimization of organic solar cells. In our group, we examine light incoupling of different kinds of transparent contacting materials as well as external dielectric coatings, using optical simulation of thin film systems and experimental methods. Thin films of small molecules are prepared by thermal evaporation in a multi-chamber UHV system. Complex refraction indices of various materials are calculated from reflection and transmission measurements of monolayers. For modelling of optical properties of thin film systems, we developed a numerical simulation program based on the transfer matrix method. The cell structures investigated consist of nanolayers of small molecules, using ZnPc/C60 as an acceptor-donor heterojunction. As contact materials, we compare the expensive standard material indium tin oxide (ITO) with more cost-efficient alternatives like thin Ag layers or spin-coated layers of the polymer PEDOT:PSS, and discuss the resulting cell properties. Additional dielectric layers of varying materials, like tris(8-hydroxy-quinolinate)-aluminum (Alq3) or N,N'-tetrakis(4-methoxyphenyl)-benzidine (MeO-TPD), are deposited on top of the stack and their influence on cell efficiencies is investigated.

Nuclear fusion rate of the muonic T3 molecule

International Nuclear Information System (INIS)

Faghihi, F.; Eskandari, M. R.

2004-01-01

The ground state binding energy, size and effective nuclear charge of the muonic T 3 molecule are calculated using Born-Oppenheimer adiabatic approximation. The system possesses two minimum positions, one at typically muonic and the second at the atomic distances. A symmetric planar vibrational model between two minima is assumed and the approximated potential are calculated. Moreover, nuclear fusion rate calculations of the short-life molecule is carried out due to the overlap integral of the resonance nuclear compound nucleus and the molecular wave functions

Single-Photon Source for Quantum Information Based on Single Dye Molecule Fluorescence in Liquid Crystal Host

International Nuclear Information System (INIS)

Lukishova, S.G.; Knox, R.P.; Freivald, P.; McNamara, A.; Boyd, R.W.; Stroud, Jr. C.R.; Schmid, A.W.; Marshall, K.L.

2006-01-01

This paper describes a new application for liquid crystals: quantum information technology. A deterministically polarized single-photon source that efficiently produces photons exhibiting antibunching is a pivotal hardware element in absolutely secure quantum communication. Planar-aligned nematic liquid crystal hosts deterministically align the single dye molecules which produce deterministically polarized single (antibunched) photons. In addition, 1-D photonic bandgap cholesteric liquid crystals will increase single-photon source efficiency. The experiments and challenges in the observation of deterministically polarized fluorescence from single dye molecules in planar-aligned glassy nematic-liquid-crystal oligomer as well as photon antibunching in glassy cholesteric oligomer are described for the first time

Light-induced magnetoresistance in solution-processed planar hybrid devices measured under ambient conditions

Directory of Open Access Journals (Sweden)

Sreetama Banerjee

2017-07-01

Full Text Available We report light-induced negative organic magnetoresistance (OMAR measured in ambient atmosphere in solution-processed 6,13-bis(triisopropylsilylethynylpentacene (TIPS-pentacene planar hybrid devices with two different device architectures. Hybrid electronic devices with trench-isolated electrodes (HED-TIE having a channel length of ca. 100 nm fabricated in this work and, for comparison, commercially available pre-structured organic field-effect transistor (OFET substrates with a channel length of 20 µm were used. The magnitude of the photocurrent as well as the magnetoresistance was found to be higher for the HED-TIE devices because of the much smaller channel length of these devices compared to the OFETs. We attribute the observed light-induced negative magnetoresistance in TIPS-pentacene to the presence of electron–hole pairs under illumination as the magnetoresistive effect scales with the photocurrent. The magnetoresistance effect was found to diminish over time under ambient conditions compared to a freshly prepared sample. We propose that the much faster degradation of the magnetoresistance effect as compared to the photocurrent was due to the incorporation of water molecules in the TIPS-pentacene film.

Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules

DEFF Research Database (Denmark)

Hubert, Mickaël; Hedegård, Erik D.; Jensen, Hans Jørgen Aa

2016-01-01

-srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2......Computational methods that can accurately and effectively predict all types of electronic excitations for any molecular system are missing in the toolbox of the computational chemist. Although various Kohn-Sham density-functional methods (KS-DFT) fulfill this aim in some cases, they become...... and double excitations have been promising, it is nevertheless important that the accuracy of MC-srDFT is at least comparable to the best KS-DFT methods also for organic molecules that are typically of single-reference character. In this paper we therefore systematically investigate the performance of MC...

Recent Advances in the Inverted Planar Structure of Perovskite Solar Cells.

Science.gov (United States)

Meng, Lei; You, Jingbi; Guo, Tzung-Fang; Yang, Yang

2016-01-19

Inorganic-organic hybrid perovskite solar cells research could be traced back to 2009, and initially showed 3.8% efficiency. After 6 years of efforts, the efficiency has been pushed to 20.1%. The pace of development was much faster than that of any type of solar cell technology. In addition to high efficiency, the device fabrication is a low-cost solution process. Due to these advantages, a large number of scientists have been immersed into this promising area. In the past 6 years, much of the research on perovskite solar cells has been focused on planar and mesoporous device structures employing an n-type TiO2 layer as the bottom electron transport layer. These architectures have achieved champion device efficiencies. However, they still possess unwanted features. Mesoporous structures require a high temperature (>450 °C) sintering process for the TiO2 scaffold, which will increase the cost and also not be compatible with flexible substrates. While the planar structures based on TiO2 (regular structure) usually suffer from a large degree of J-V hysteresis. Recently, another emerging structure, referred to as an "inverted" planar device structure (i.e., p-i-n), uses p-type and n-type materials as bottom and top charge transport layers, respectively. This structure derived from organic solar cells, and the charge transport layers used in organic photovoltaics were successfully transferred into perovskite solar cells. The p-i-n structure of perovskite solar cells has shown efficiencies as high as 18%, lower temperature processing, flexibility, and, furthermore, negligible J-V hysteresis effects. In this Account, we will provide a comprehensive comparison of the mesoporous and planar structures, and also the regular and inverted of planar structures. Later, we will focus the discussion on the development of the inverted planar structure of perovskite solar cells, including film growth, band alignment, stability, and hysteresis. In the film growth part, several

Luminescence of Rubrene and DCJTB molecules in organic light-emitting devices

Energy Technology Data Exchange (ETDEWEB)

Moon, Chang-Bum, E-mail: cbmoon@hoseo.edu [Department of Display Engineering, Hoseo University, Sechul-Ri 160, Baebang, Asan, Chung-Nam 336-795 (Korea, Republic of); Department of Engineering Physics, McMaster University, Hamilton, Ontario, Canada L8S4L7 (Canada); Song, Wook; Meng, Mei; Kim, Nam Ho; Yoon, Ju-An [Department of Display Engineering, Hoseo University, Sechul-Ri 160, Baebang, Asan, Chung-Nam 336-795 (Korea, Republic of); Kim, Woo Young, E-mail: wykim@hoseo.edu [Department of Display Engineering, Hoseo University, Sechul-Ri 160, Baebang, Asan, Chung-Nam 336-795 (Korea, Republic of); Wood, Richard; Mascher, Peter [Department of Engineering Physics, McMaster University, Hamilton, Ontario, Canada L8S4L7 (Canada)

2014-02-15

We investigated the optical properties of light emission based on the resonance energy transfer mechanism between two molecules in the host–dopant systems. For this purpose, we fabricated the organic light-emitting devices with the different doped emissive layers. The host matrices were made of 4,4′,4″-tris(carbasol-l-nyl)triphenylamine (TCTA) and 2-methyl-9,10-di(2-naphthyl)anthracene (MADN) molecules and the doped molecules were 5,6,11,12-tetraphenylnaphtacene (Rubrene) and 4-(Dicyanomethylene)-2-tert-butyl-6- (1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB). The concentrations of the doped molecules were 0.1%, 0.3%, 0.5%, and 0.8%. Through spectroscopic analysis using multi-peak fits with a Gaussian function to the emission spectra, we obtained the relative light intensity of the two dopants according to the doping concentrations and examined the relations between the molecular excited energy states and the nature of energy transfer in the host and dopant systems. We show that the luminous efficiency of the devices has a strong correlation between the energy transfer owing to the individual molecular intrinsic properties and the electrical characteristics associated with the bulky properties in the devices. -- Highlights: • Fabrication and characterization of the OLEDs with a host–dopant system in the emissive layer. • Investigation of the optical properties of light emission based on the resonance energy transfer mechanism between the dopant molecules. • EL and PL spectroscopic study for the structure of the molecular energy levels in the dopant molecules.

Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

Energy Technology Data Exchange (ETDEWEB)

Pan, Shanlin [Univ. of Alabama, Tuscaloosa, AL (United States)

2014-11-16

Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest that the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an

Oxidative addition of C--H bonds in organic molecules to transition metal centers

International Nuclear Information System (INIS)

Bergman, R.G.

1989-04-01

Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs

On the genetic control of planar growth during tissue morphogenesis in plants.

Science.gov (United States)

Enugutti, Balaji; Kirchhelle, Charlotte; Schneitz, Kay

2013-06-01

Tissue morphogenesis requires extensive intercellular communication. Plant organs are composites of distinct radial cell layers. A typical layer, such as the epidermis, is propagated by stereotypic anticlinal cell divisions. It is presently unclear what mechanisms coordinate cell divisions relative to the plane of a layer, resulting in planar growth and maintenance of the layer structure. Failure in the regulation of coordinated growth across a tissue may result in spatially restricted abnormal growth and the formation of a tumor-like protrusion. Therefore, one way to approach planar growth control is to look for genetic mutants that exhibit localized tumor-like outgrowths. Interestingly, plants appear to have evolved quite robust genetic mechanisms that govern these aspects of tissue morphogenesis. Here we provide a short summary of the current knowledge about the genetics of tumor formation in plants and relate it to the known control of coordinated cell behavior within a tissue layer. We further portray the integuments of Arabidopsis thaliana as an excellent model system to study the regulation of planar growth. The value of examining this process in integuments was established by the recent identification of the Arabidopsis AGC VIII kinase UNICORN as a novel growth suppressor involved in the regulation of planar growth and the inhibition of localized ectopic growth in integuments and other floral organs. An emerging insight is that misregulation of central determinants of adaxial-abaxial tissue polarity can lead to the formation of spatially restricted multicellular outgrowths in several tissues. Thus, there may exist a link between the mechanisms regulating adaxial-abaxial tissue polarity and planar growth in plants.

Core Level Spectra of Organic Molecules Adsorbed on Graphene

Directory of Open Access Journals (Sweden)

Abhilash Ravikumar

2018-03-01

Full Text Available We perform first principle calculations based on density functional theory to investigate the effect of the adsorption of core-excited organic molecules on graphene. We simulate Near Edge X-ray absorption Fine Structure (NEXAFS and X-ray Photoemission Spectroscopy (XPS at the N and C edges for two moieties: pyridine and the pyridine radical on graphene, which exemplify two different adsorption characters. The modifications of molecular and graphene energy levels due to their interplay with the core-level excitation are discussed. We find that upon physisorption of pyridine, the binding energies of graphene close to the adsorption site reduce mildly, and the NEXAFS spectra of the molecule and graphene resemble those of gas phase pyridine and pristine graphene, respectively. However, the chemisorption of the pyridine radical is found to significantly alter these core excited spectra. The C 1s binding energy of the C atom of graphene participating in chemisorption increases by ∼1 eV, and the C atoms of graphene alternate to the adsorption site show a reduction in the binding energy. Analogously, these C atoms also show strong modifications in the NEXAFS spectra. The NEXAFS spectrum of the chemisorbed molecule is also modified as a result of hybridization with and screening by graphene. We eventually explore the electronic properties and magnetism of the system as a core-level excitation is adiabatically switched on.

Theory of photoelectron spectroscopy for organic molecules and their crystals

Energy Technology Data Exchange (ETDEWEB)

Fujikawa, Takashi, E-mail: tfujikawa@faculty.chiba-u.jp; Niki, Kaori; Sakuma, Hiroto

2015-10-01

Highlights: • Some specific features in photoemission theory from organic solids are reviewed. • Extrinsic and intrinsic effects are discussed. • Photoemission from extended levels is compared with that from core levels. • First principle many-body theories are discussed on the basis of nonequilibrium Green's functions. - Abstract: In this short review we discuss recent progress in photoemission theory for organic molecules and their crystals. We discuss some important features in Keldysh Green's function theory for the photoemission. We briefly discuss many-body aspects in photoemission from core and extended levels. In particular phonon effects are investigated in more detail since organic solids are typically soft where electron–phonon interaction is important. Debye–Waller factor suppresses the interference effects of photoelectron waves which makes ARPES analyses useless, particularly in high energy region.

CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

Energy Technology Data Exchange (ETDEWEB)

Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H. [LISA Laboratoire Interuniversitaire des Systèmes Atmosphériques, UMR CNRS 7583, Université Paris Est Créteil (UPEC), Université Paris Diderot (UPD), Institut Pierre Simon Laplace, Labex ESEP, Paris (France); Duvernay, F.; Chiavassa, T., E-mail: vvinogradoff@mnhn.fr [PIIM, Laboratoire de Physique des Interactions Ioniques et Moléculaires, Université Aix-Marseille, UMR CNRS 7345, Marseille (France)

2015-08-20

Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H{sub 2}O, NH{sub 3}, CO{sub 2}, H{sub 2}CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites.

CARBON DIOXIDE INFLUENCE ON THE THERMAL FORMATION OF COMPLEX ORGANIC MOLECULES IN INTERSTELLAR ICE ANALOGS

International Nuclear Information System (INIS)

Vinogradoff, V.; Fray, N.; Bouilloud, M.; Cottin, H.; Duvernay, F.; Chiavassa, T.

2015-01-01

Interstellar ices are submitted to energetic processes (thermal, UV, and cosmic-ray radiations) producing complex organic molecules. Laboratory experiments aim to reproduce the evolution of interstellar ices to better understand the chemical changes leading to the reaction, formation, and desorption of molecules. In this context, the thermal evolution of an interstellar ice analogue composed of water, carbon dioxide, ammonia, and formaldehyde is investigated. The ice evolution during the warming has been monitored by IR spectroscopy. The formation of hexamethylenetetramine (HMT) and polymethylenimine (PMI) are observed in the organic refractory residue left after ice sublimation. A better understanding of this result is realized with the study of another ice mixture containing methylenimine (a precursor of HMT) with carbon dioxide and ammonia. It appears that carbamic acid, a reaction product of carbon dioxide and ammonia, plays the role of catalyst, allowing the reactions toward HMT and PMI formation. This is the first time that such complex organic molecules (HMT, PMI) are produced from the warming (without VUV photolysis or irradiation with energetic particles) of abundant molecules observed in interstellar ices (H 2 O, NH 3 , CO 2 , H 2 CO). This result strengthens the importance of thermal reactions in the ices’ evolution. HMT and PMI, likely components of interstellar ices, should be searched for in the pristine objects of our solar system, such as comets and carbonaceous chondrites

Complex organic molecules toward low-mass and high-mass star forming regions

Science.gov (United States)

Favre, C.; Ceccarelli, C.; Lefloch, B.; Bergin, E.; Carvajal, M.; Brouillet, N.; Despois, D.; Jørgensen, J.; Kleiner, I.

2016-12-01

One of the most important questions in molecular astrophysics is how, when, and where complex organic molecules, COMs (≥ 6 atoms) are formed. In the Interstellar-Earth connection context, could this have a bearing on the origin of life on Earth? Formation mechanisms of COMs, which include potentially prebiotic molecules, are still debated and may include grain-mantle and/or gas-phase chemistry. Understanding the mechanisms that lead to the interstellar molecular complexification, along with the involved physicochemical processes, is mandatory to answer the above questions. In that context, active researches are ongoing in theory, laboratory experiment, chemical modeling and observations. Thanks to recent progress in radioastronomy instrumentation for both single-dish and millimeter array (e.g. Herschel, NOEMA, ALMA), new results have been obtained. I will review some notable results on the detection of COMs, including prebiotic molecules, towards star forming regions.

Isotope-selective high-order interferometry with large organic molecules in free fall

Science.gov (United States)

Rodewald, Jonas; Dörre, Nadine; Grimaldi, Andrea; Geyer, Philipp; Felix, Lukas; Mayor, Marcel; Shayeghi, Armin; Arndt, Markus

2018-03-01

Interferometry in the time domain has proven valuable for matter-wave based measurements. This concept has recently been generalized to cold molecular clusters using short-pulse standing light waves which realized photo-depletion gratings, arranged in a time-domain Talbot–Lau interferometer (OTIMA). Here we extend this idea further to large organic molecules and demonstrate a new scheme to scan the emerging molecular interferogram in position space. The capability of analyzing different isotopes of the same monomer under identical conditions opens perspectives for studying the interference fringe shift as a function of time in gravitational free fall. The universality of OTIMA interferometry allows one to handle a large variety of particles. In our present work, quasi-continuous laser evaporation allows transferring fragile organic molecules into the gas phase, covering more than an order of magnitude in mass between 614 amu and 6509 amu, i.e. 300% more massive than in previous OTIMA experiments. For all masses, we find about 30% fringe visibility.

On structure of some laminated crystals with organic molecules

International Nuclear Information System (INIS)

Volodina, G.F.; Ivanova, V.Ya.; Malinovskij, T.I.

1982-01-01

A survey is made of papers dealing with intercalation of organic molecules into crystals of dihalcogenides of some transition metals (TaS 2 , TiS 2 , NbS 2 , ZrS 2 , TaSe 2 ), variation of their structure and physical properties. Among the used intercalates ammonia, pyridine, aniline and other aromatic amines proved to be most satisfactory from the viewpoint of reaction rate and product stability. A possibility is discussed of intercalation into PbI 2 and CdI 2 crystals that are of the same structural type as dihalcogenides

How to draw a planarization

NARCIS (Netherlands)

Bläsius, T.; Radermacher, M.; Rutter, I.; Steffen, B.; Baier, C.; van den Brand, M.; Eder, J.; Hinchey, M.; Margaria, T.

2017-01-01

We study the problem of computing straight-line drawings of non-planar graphs with few crossings. We assume that a crossing-minimization algorithm is applied first, yielding a planarization, i.e., a planar graph with a dummy vertex for each crossing, that fixes the topology of the resulting drawing.

Acenes, Heteroacenes and Analogous Molecules for Organic Photovoltaic and Field Effect Transistor Applications

Science.gov (United States)

Granger, Devin Benjamin

Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have likewise been investigated. Functionalization of acene compounds by placement of groups around the molecule affects the way in which molecules interact in the solid state, in addition to the energetics of the molecule. The use of electron donating or electron withdrawing groups affects the frontier molecular orbitals and thus affects the optical and electronic gaps of the molecules. The use of bulky side groups such as alkylsilylethynyl groups allows for crystal engineering of molecular aggregates, and changing the volume and dimensions of the alkylsilyl groups affects the intermolecular interactions and thus changes the packing motif. In chapter 2, a series of tetracene and pentacene molecules with strongly electron withdrawing groups is described. The investigation focuses on the change in energetics of the frontier molecular orbitals between the base acene and the nitrile and dicyanovinyl derivatives as well as the differences between the pentacene and tetracene molecules. The differences in close packing motifs through use of bulky alkylsilylethynyl groups is also discussed in relation to electron acceptor material design and bulk heterojunction organic photovoltaic characteristics. Chapter 3 focuses on molecular acceptor and

Design of special planar linkages

CERN Document Server

Zhao, Jing-Shan; Ma, Ning; Chu, Fulei

2013-01-01

Planar linkages play a very important role in mechanical engineering. As the simplest closed chain mechanisms, planar four-bar linkages are widely used in mechanical engineering, civil engineering and aerospace engineering.Design of Special Planar Linkages proposes a uniform design theory for planar four-bar linkages. The merit of the method proposed in this book is that it allows engineers to directly obtain accurate results when there are such solutions for the specified n precise positions; otherwise, the best approximate solutions will be found. This book discusses the kinematics and reach

Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules.

Science.gov (United States)

Jacquemin, Denis; Wathelet, Valérie; Perpète, Eric A; Adamo, Carlo

2009-09-08

Extensive Time-Dependent Density Functional Theory (TD-DFT) calculations have been carried out in order to obtain a statistically meaningful analysis of the merits of a large number of functionals. To reach this goal, a very extended set of molecules (∼500 compounds, >700 excited states) covering a broad range of (bio)organic molecules and dyes have been investigated. Likewise, 29 functionals including LDA, GGA, meta-GGA, global hybrids, and long-range-corrected hybrids have been considered. Comparisons with both theoretical references and experimental measurements have been carried out. On average, the functionals providing the best match with reference data are, one the one hand, global hybrids containing between 22% and 25% of exact exchange (X3LYP, B98, PBE0, and mPW1PW91) and, on the other hand, a long-range-corrected hybrid with a less-rapidly increasing HF ratio, namely LC-ωPBE(20). Pure functionals tend to be less consistent, whereas functionals incorporating a larger fraction of exact exchange tend to underestimate significantly the transition energies. For most treated cases, the M05 and CAM-B3LYP schemes deliver fairly small deviations but do not outperform standard hybrids such as X3LYP or PBE0, at least within the vertical approximation. With the optimal functionals, one obtains mean absolute deviations smaller than 0.25 eV, though the errors significantly depend on the subset of molecules or states considered. As an illustration, PBE0 and LC-ωPBE(20) provide a mean absolute error of only 0.14 eV for the 228 states related to neutral organic dyes but are completely off target for cyanine-like derivatives. On the basis of comparisons with theoretical estimates, it also turned out that CC2 and TD-DFT errors are of the same order of magnitude, once the above-mentioned hybrids are selected.

Retention of U(VI) onto silica in presence of model organic molecules

International Nuclear Information System (INIS)

Pham, T.T.H.; Mercier-Bion, F.; Drot, R.; Lagarde, G.; Simoni, E.; Lambert, J.

2008-01-01

It is well-known that the organic matter influences the retention of ions onto mineral surfaces. However, the major part of concerned studies implies humic substances and complex solids. Another approach for identifying the sorption mechanisms is possible by studying simpler solids than those present in natural medium. So, silica is chosen as mineral surface because of its abundance in soils and of the presence of Si-O groups in clayey minerals. Uranium (VI) is selected as cation. Simple organic molecules like acetic (one carboxylic group) and oxalic (two carboxylic functions) acids are considered as models of the natural organic matter for understanding their role in the retention of U(VI) onto powders and slides of silica. Binary (organics/silica, U(VI)/silica) and ternary systems (organics/silica/U(VI)) are studied by complementary approaches. Sorption edges as function of pH are obtained by liquid scintillation methods and capillary electrophoresis. Different spectroscopic techniques are used to deduce the interactions between the organic matter and U(VI) sorbed onto the silica whose: Time-Resolved Laser induced Fluorescence Spectroscopy (TRLFS), X-ray Photoelectron Spectroscopy (XPS), Nuclear Microprobe Analysis (NMA). The results of the effect of these model organic molecules onto the U(VI) retention showed a good agreement between the different techniques. Concerning the acetic acid, there are not differences in the sorption percentages of uranyl (see the figure). All these results indicate that the uranyl-acetate complexes stay in the aqueous solution rather than sorbing onto the silica. On the contrary, oxalic acid influences the sorption of U(VI) onto the silica surface. The sorption percentage of U(VI) in the ternary system (oxalic acid/silica/U(VI)) is lower than the binary system (U(VI)/silica) (see the figure). So, the presence of oxalic acid decreases the sorption of U(VI) onto the silica surface. (authors)

Instantaneous temperature field measurements using planar laser-induced fluorescence.

Science.gov (United States)

Seitzman, J M; Kychakoff, G; Hanson, R K

1985-09-01

A single-pulse, laser-induced-fluorescence diagnostic for the measurement of two-dimensional temperature fields in combustion flows is described. The method uses sheet illumination from a tunable laser to excite planar laserinduced fluorescence in a stable tracer molecule, seeded at constant mole fraction into the flow field. The temporal resolution of this technique is determined by the laser pulse length. Experimental results are presented for a rodstabilized, premixed methane-air flame, using the Q(1) (22) line of the nitric oxide A(2) Sigma(+) (v = 0) ? X(2)II((1/2))(v = 0) transition (lambda approximately 225.6 nm).

On the SIMS Ionization Probability of Organic Molecules.

Science.gov (United States)

Popczun, Nicholas J; Breuer, Lars; Wucher, Andreas; Winograd, Nicholas

2017-06-01

The prospect of improved secondary ion yields for secondary ion mass spectrometry (SIMS) experiments drives innovation of new primary ion sources, instrumentation, and post-ionization techniques. The largest factor affecting secondary ion efficiency is believed to be the poor ionization probability (α + ) of sputtered material, a value rarely measured directly, but estimated to be in some cases as low as 10 -5 . Our lab has developed a method for the direct determination of α + in a SIMS experiment using laser post-ionization (LPI) to detect neutral molecular species in the sputtered plume for an organic compound. Here, we apply this method to coronene (C 24 H 12 ), a polyaromatic hydrocarbon that exhibits strong molecular signal during gas-phase photoionization. A two-dimensional spatial distribution of sputtered neutral molecules is measured and presented. It is shown that the ionization probability of molecular coronene desorbed from a clean film under bombardment with 40 keV C 60 cluster projectiles is of the order of 10 -3 , with some remaining uncertainty arising from laser-induced fragmentation and possible differences in the emission velocity distributions of neutral and ionized molecules. In general, this work establishes a method to estimate the ionization efficiency of molecular species sputtered during a single bombardment event. Graphical Abstract GRAPHICAL ABSTRACT TEXT HERE] -->.

Structure of the Buried Metal-Molecule Interface in Organic Thin Film Devices

DEFF Research Database (Denmark)

Hansen, Christian Rein; Sørensen, Thomas Just; Glyvradal, Magni

2009-01-01

By use of specular X-ray reflectivity (XR) the structure of a metal-covered organic thin film device is measured with angstrom resolution. The model system is a Langmuir-Blodgett (LB) film, sandwiched between a silicon substrate and a top electrode consisting of 25 Å titanium and 100 Å aluminum....... By comparison of XR data for the five-layer Pb2+ arachidate LB film before and after vapor deposition of the Ti/Al top electrode, a detailed account of the structural damage to the organic film at the buried metal-molecule interface is obtained. We find that the organized structure of the two topmost LB layers...

Cometary delivery of organic molecules to the early earth

Science.gov (United States)

Chyba, Christopher F.; Thomas, Paul J.; Sagan, Carl; Brookshaw, Leigh

1990-01-01

It has long been speculated that earth accreted prebiotic organic molecules important for the origins of life from impacts of carbonaceous asteroids and comets during the period of heavy bombardment 4.5 x 10 to the 9th to 3.8 x 10 to the 9th years ago. A comprehensive treatment of comet-asteroid interaction with the atmosphere, surface impact, and resulting organic pyrolysis demonstrates that organics will not survive impacts at velocities greater than about 10 kilometers per second and that even comets and asteroids as small as 100 meters in radius cannot be aerobraked to below this velocity in 1-bar atmospheres. However, for plausible dense (10-bar carbon dioxide) early atmospheres, it is found that 4.5 x 10 to the 9th years ago earth was accreting intact cometary organics at a rate of at least about 10 to the 6th to 10 to the 7th kilograms per year, a flux that thereafter declined with a half-life of about 10 to the 8th years. These results may be put in context by comparison with terrestrial oceanic and total biomasses, about 3 x 10 to the 12th kilograms and about 6 x 10 to the 14th kilograms, respectively.

Late stage crystallization and healing during spin-coating enhance carrier transport in small-molecule organic semiconductors

KAUST Repository

Chou, Kang Wei; Khan, Hadayat Ullah; Niazi, Muhammad Rizwan; Yan, Buyi; Li, Ruipeng; Payne, Marcia M.; Anthony, John Edward; Smilgies, Detlef Matthias; Amassian, Aram

2014-01-01

Spin-coating is currently the most widely used solution processing method in organic electronics. Here, we report, for the first time, a direct investigation of the formation process of the small-molecule organic semiconductor (OSC) 6,13-bis

Atomic-Resolution Transmission Electron Microscopic Movies for Study of Organic Molecules, Assemblies, and Reactions: The First 10 Years of Development.

Science.gov (United States)

Nakamura, Eiichi

2017-06-20

A molecule is a quantum mechanical entity. "Watching motions and reactions of a molecule with our eyes" has therefore been a dream of chemists for a century. This dream has come true with the aid of the movies of atomic-resolution transmission electron microscopic (AR-TEM) molecular images through real-time observation of dynamic motions of single organic molecules (denoted hereafter as single-molecule atomic-resolution real-time (SMART) TEM imaging). Since 2007, we have reported movies of a variety of single organic molecules, organometallic molecules, and their assemblies, which are rotating, stretching, and reacting. Like movies in the theater, the atomic-resolution molecular movies provide us information on the 3-D structures of the molecules and also their time evolution. The success of the SMART-TEM imaging crucially depends on the development of "chemical fishhooks" with which fish (organic molecules) in solution can be captured on a single-walled carbon nanotube (CNT, serving as a "fishing rod"). The captured molecules are connected to a slowly vibrating CNT, and their motions are displayed on a monitor in real time. A "fishing line" connecting the fish and the rod may be a σ-bond, a van der Waals force, or other weak connections. Here, the molecule/CNT system behaves as a coupled oscillator, where the low-frequency anisotropic vibration of the CNT is transmitted to the molecules via the weak chemical connections that act as an energy filter. Interpretation of the observed motions of the molecules at atomic resolution needs us to consider the quantum mechanical nature of electrons as well as bond rotation, letting us deviate from the conventional statistical world of chemistry. What new horizons can we explore? We have so far carried out conformational studies of individual molecules, assigning anti or gauche conformations to each C-C bond in conformers that we saw. We can also determine the structures of van der Waals assemblies of organic molecules

Searching for Bio-Precursors and Complex Organic Molecules in Space using the GBT

Science.gov (United States)

Cordiner, M.; Charnley, S.; Kisiel, Z.

2012-01-01

Using the latest microwave receiver technology, large organic molecules with abundances as low as approx. 10(exp -11) times that of molecular hydrogen are detectable in cold interstellar clouds via their rotational emission line spectra. We report new observations to search for complex molecules, including molecules of possible pre-biotic importance, using the newly-commissioned Kband focal plane array (KFPA) of the NRAO Robert C. Byrd Green Bank Telescope. Spectra are presented of the dense molecular cloud TMC-1, showing strict upper limits on the level of emission from nitrogen-bearing rings pyrimidine, quinoline and iso-quinoline, carbon-chain oxides C60, C70, HC60 and HC70, and the carbon-chain anion C4H-. The typical RMS brightness temperature noise levels we achieved are approx. 1 mK at around 20 GHz.

Hydrophilicity and Microsolvation of an Organic Molecule Resolved on the Sub-molecular Level by Scanning Tunneling Microscopy.

Science.gov (United States)

Lucht, Karsten; Loose, Dirk; Ruschmeier, Maximilian; Strotkötter, Valerie; Dyker, Gerald; Morgenstern, Karina

2018-01-26

Low-temperature scanning tunneling microscopy was used to follow the formation of a solvation shell around an adsorbed functionalized azo dye from the attachment of the first water molecule to a fully solvated molecule. Specific functional groups bind initially one water molecule each, which act as anchor points for additional water molecules. Further water attachment occurs in areas close to these functional groups even when the functional groups themselves are already saturated. In contrast, water molecules surround the hydrophobic parts of the molecule only when the two-dimensional solvation shell closes around them. This study thus traces hydrophilic and hydrophobic properties of an organic molecule down to a sub-molecular length scale. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal chemistry of uranyl carboxylate coordination networks obtained in the presence of organic amine molecules

Energy Technology Data Exchange (ETDEWEB)

Mihalcea, Ionut; Henry, Natacha; Loiseau, Thierry [Unite de Catalyse et Chimie du Solide (UCCS) - UMR CNRS 8181, Universite de Lille Nord de France, USTL-ENSCL, Villeneuve d' Ascq (France)

2014-03-15

Three uranyl isophthalates (1,3-bdc) and two uranyl pyromellitates (btec) of coordination-polymer type were hydrothermally synthesized (200 C for 24 h) in the presence of different amine-based molecules [1,3-diaminopropane (dap) or dimethylamine (dma) originating from the in situ decomposition of N,N-dimethylformamide]. (UO{sub 2}){sub 2}(OH){sub 2}(H{sub 2}O)(1,3-bdc).H{sub 2}O (1) is composed of inorganic tetranuclear cores, which are linked to each other through the isophthalato ligand to generate infinite neutral ribbons, which are intercalated by free H{sub 2}O molecules. The compounds (UO{sub 2}){sub 1.5}(H{sub 2}O)(1,3-bdc){sub 2}.0.5H{sub 2}dap.1.5H{sub 2}O (2) and UO{sub 2}(1,3-bdc){sub 1.5}.0.5H{sub 2}dap.2H{sub 2}O (3) consist of discrete uranyl-centered hexagonal bipyramids connected to each other by a ditopic linker to form a single-layer network for 2 or a double-layer network for 3. The protonated diamine molecules are located between the uranyl-organic sheets and balance the negative charge of the layered sub-networks. The phase (UO{sub 2}){sub 2}O(btec).2Hdma.H{sub 2}O (4) presents a 2D structure built up from tetranuclear units, which consist of two central sevenfold coordinated uranium centers and two peripheral eightfold coordinated uranium centers. The connection of the resulting tetramers through the pyromellitate molecules generates an anionic layerlike structure, in which the protonated dimethylammonium species are inserted. The compound UO{sub 2}(btec).2Hdma (5) is also a lamellar coordination polymer, which contains isolated eightfold coordinated uranium cations linked through pyromellitate molecules and intercalated by protonated dimethylammonium species. In both phases 4 and 5, the btec linker has non-bonded carboxyl oxygen atoms, which preferentially interact with the protonated amine molecules through a hydrogen-bond network. The different illustrations show the structural diversity of uranyl-organic coordination polymers with organic

Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

International Nuclear Information System (INIS)

Paul, Manidipa; Pal, Nabanita; Bhaumik, Asim

2012-01-01

Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6–7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate–adsorbent interaction at the surfaces. - Graphical abstract: Highly ordered 2D-hexagonal mesoporous borosilicate materials have been synthesized by using Pluronic P123 as template. The materials show very good adsorption and release of organic cationic dye molecules under physiological conditions. Highlights: ► Highly ordered 2D-hexagonal mesoporous borosilicate. ► Nonionic Pluoronic P123 templated mesoporous material. ► Adsorption of organic dyes at the mesopore surface. ► Controlled release of dyes under physiological pH and temperature. ► Release of safranine T (ST) and malachite green (MG) dyes in simulated body fluids.

The Effects of Perchlorate and its Precursors on Organic Molecules under Simulated Mars Conditions

Science.gov (United States)

Carrier, B. L.; Beegle, L. W.; Bhartia, R.; Abbey, W. J.

2016-12-01

Perchlorate (ClO4-) was first detected on Mars by the Phoenix Lander in 2008 [1] and has subsequently been detected by Curiosity in Gale Crater [2], in Mars meteorite EETA79001 [3], and has been proposed as a possible explanation for results obtained by Viking [4]. Perchlorate has also been shown to be formed under current Mars conditions via the oxidation of mineral chlorides, further supporting the theory that perchlorate is present globally on Mars [5]. The discovery of perchlorate on Mars has raised important questions about its effects on the survival and detection of organic molecules. Although it has been shown that pyrolysis in the presence of perchlorate results in the alteration or destruction of organic molecules [2, 4], few studies have been conducted on the potential effects of perchlorate and its precursors on organic molecules prior to analysis. Perchlorate is typically inert under Mars temperatures and pressures, but it has been shown to decompose to form reactive oxychlorine species such as chlorite (ClO2-), hypochlorite (ClO-) and chlorine dioxide (ClO2) when exposed to Mars conditions including ionizing radiation [6]. The oxidation of chloride to perchlorate also results in the formation of reactive oxychlorine species such as chlorate (ClO3-) [5]. Here we investigate the effects of perchlorate and its oxychlorine precursors on organic molecules. Experiments are performed in a Mars Simulation Chamber (MSC) capable of reproducing the temperature, pressure, atmospheric composition and UV flux found on Mars. Soil simulants are prepared consisting of Mojave Mars Simulant (MMS) [7] and each organic, as well as varying concentrations of perchlorate and/or chloride salts, and exposed in the MSC. Subsequent to exposure in the MSC samples are leached and the leachate analyzed by HPLC and LC-MS to determine the degree of degradation of the original organic and the identity of any potential decomposition products formed by oxidation or chlorination

Non-planar ABJ theory and parity

International Nuclear Information System (INIS)

Caputa, Pawel; Kristjansen, Charlotte; Zoubos, Konstantinos

2009-01-01

While the ABJ Chern-Simons-matter theory and its string theory dual manifestly lack parity invariance, no sign of parity violation has so far been observed on the weak coupling spin chain side. In particular, the planar two-loop dilatation generator of ABJ theory is parity invariant. In this Letter we derive the non-planar part of the two-loop dilatation generator of ABJ theory in its SU(2)xSU(2) sub-sector. Applying the dilatation generator to short operators, we explicitly demonstrate that, for operators carrying excitations on both spin chains, the non-planar part breaks parity invariance. For operators with only one type of excitation, however, parity remains conserved at the non-planar level. We furthermore observe that, as for ABJM theory, the degeneracy between planar parity pairs is lifted when non-planar corrections are taken into account.

Non-planar ABJ Theory and Parity

DEFF Research Database (Denmark)

Caputa, Pawel; Kristjansen, Charlotte; Zoubos, Konstantinos

2009-01-01

we derive the non-planar part of the two-loop dilatation generator of ABJ theory in its SU(2)xSU(2) sub-sector. Applying the dilatation generator to short operators, we explicitly demonstrate that, for operators carrying excitations on both spin chains, the non-planar part breaks parity invariance......While the ABJ Chern-Simons-matter theory and its string theory dual manifestly lack parity invariance, no sign of parity violation has so far been observed on the weak coupling spin chain side. In particular, the planar two-loop dilatation generator of ABJ theory is parity invariant. In this letter....... For operators with only one type of excitation, however, parity remains conserved at the non-planar level. We furthermore observe that, as for ABJM theory, the degeneracy between planar parity pairs is lifted when non-planar corrections are taken into account....

Application of terahertz spectroscopy for characterization of biologically active organic molecules in natural environment

Science.gov (United States)

Karaliūnas, Mindaugas; Jakštas, Vytautas; Nasser, Kinan E.; Venckevičius, Rimvydas; Urbanowicz, Andrzej; Kašalynas, Irmantas; Valušis, Gintaras

2016-09-01

In this work, a comparative research of biologically active organic molecules in its natural environment using the terahertz (THz) time domain spectroscopy (TDS) and Fourier transform spectroscopy (FTS) systems is carried out. Absorption coefficient and refractive index of Nicotiana tabacum L. leaves containing nicotine, Cannabis sativa L. leaves containing tetrahydrocannabinol, and Humulu lupulus L. leaves containing α-acids, active organic molecules that obtain in natural environment, were measured in broad frequency range from 0.1 to 13 THz at room temperature. In the spectra of absorption coefficient the features were found to be unique for N. tabacum, C. sativa and H. lupulus. Moreover, those features can be exploited for identification of C. sativa sex and N. tabacum origin. The refractive index can be also used to characterize different species.

Expert systems for structure elucidation of organic molecules by spectral methods

International Nuclear Information System (INIS)

Elyashberg, Mikhail E

1999-01-01

The state-of-the-art of the investigations aimed at creating expert systems for establishing the structure of organic molecules from IR, 1 H and 13 C NMR spectra is analysed. Computer methods used for identification of molecular fragments, generation of their structure and spectra prediction are considered. Principles of the creation of modern expert systems and general strategy of solving structural problems are discussed. The bibliography includes 174 references.

Predicting Complex Organic Molecule Emission from TW Hya

Science.gov (United States)

Vissapragada, Shreyas; Walsh, Catherine

2017-01-01

The Atacama Large Millimeter/submillimeter Array (ALMA) has significantly increased our ability to observe the rich chemical inventory of star and planet formation. ALMA has recently been used to detect CH3OH (methanol) and CH3CN (methyl cyanide) in protoplanetary disks; these molecules may be vital indicators of the complex organic ice reservoir in the comet-forming zone. We have constructed a physiochemical model of TW Hya, a well-studied protoplanetary disk, to explore the different formation mechanisms of complex ices. By running our model through a radiative transfer code and convolving with beam sizes appropriate for ALMA, we have obtained synthetic observations of methanol and methyl cyanide. Here, we compare and comment on these synthetic observations, and provide astrochemical justification for their spatial distributions.

Functionalization of nanoparticle titanium dioxide with different bifunctional organic molecules and trimers of transition compounds for obtaining new materials

International Nuclear Information System (INIS)

Rivera Martinez, Maria Cinthya

2012-01-01

Functionalization of titanium dioxide in nanoporous anatase phase is investigated for obtaining new nanomaterials. Functionalizations were performed using two heating methods: the conventional of refluxing heating method and microwave irradiation with bifunctional organic molecules is used to study how to anchor molecules and the change in the wettability of the material. Besides, reactions with organic molecules were performed as the derived from nanoproxene. The growth layer by layer is performed using the bifunctional molecules previous for the immobilization of cobalt trimers. Functionalized molecules were characterized by infrared spectroscopy, X-ray diffraction, contact angle, scanning electron microscopy, x-ray elemental analysis, plasma atomic emission spectroscopy coupled inductively, x-ray photoelectron spectroscopy and thermogravimetric analysis. This type of functionalizations on nanoporous titanium dioxide could potentially improve optical sensitivity and activity of this nanomaterial in the visible region. (author) [es

A single molecule approach for measuring the transport properties and energetics of membrane proteins in heterogeneous planar bio-mimetic assemblies

Science.gov (United States)

Poudel, Kumud Raj

The significance of transmembrane protein research is well documented. Numerous studies have clearly established the biological, biophysical and pharmaceutical importance that these membrane components serve. Communications through receptors regulate countless body functions and they also provide structural support to the cell. However, a lack of high-resolution structure data has limited our understanding of these proteins that make it necessary to study them in in-vitro platforms or 'bio-mimetic' assemblies. Albeit that an assortment of platforms have been suggested for in-vitro studies, the issues, however, remain the same. The lack of mobility of the proteins in artificial environments, the question of functionality that arises with mobility and the search in general for the best assembly, is still a work in progress. In this work, we have taken some of the most accepted platforms in the field and characterized them through the lens of single molecule spectroscopy. We have addressed the question of mobility by reducing it down to a single molecule and comparing it with the bulk. By utilizing the Serotonin Receptor 5HT3A we have shown that techniques such as passivation of the substrates in the assemblies by Bovine Serum Albumin has a significant effect at the molecular level. The larger size of the intracellular domain for the 5HT3A served as a great probe to understand and evaluate the interaction of a surface passivator with the integrated membrane protein. We have also taken this a step further by developing a novel, single cushion 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) assembly and added another degree of complexity- through a phase transition. We have utilized phase transition to get an insight into the local protein environment, activation energies, heterogeneity and diffusion characteristics by using Annexin V as our probe. The work presented here studies two completely different biological platforms using two entirely different transmembrane

Near-unity mass accommodation coefficient of organic molecules of varying structure.

Science.gov (United States)

Julin, Jan; Winkler, Paul M; Donahue, Neil M; Wagner, Paul E; Riipinen, Ilona

2014-10-21

Atmospheric aerosol particles have a significant effect on global climate, air quality, and consequently human health. Condensation of organic vapors is a key process in the growth of nanometer-sized particles to climate relevant sizes. This growth is very sensitive to the mass accommodation coefficient α, a quantity describing the vapor uptake ability of the particles, but knowledge on α of atmospheric organics is lacking. In this work, we have determined α for four organic molecules with diverse structural properties: adipic acid, succinic acid, naphthalene, and nonane. The coefficients are studied using molecular dynamics simulations, complemented with expansion chamber measurements. Our results are consistent with α = 1 (indicating nearly perfect accommodation), regardless of the molecular structural properties, the phase state of the bulk condensed phase, or surface curvature. The results highlight the need for experimental techniques capable of resolving the internal structure of nanoparticles to better constrain the accommodation of atmospheric organics.

Functionalized Self-Assembled InAs/GaAs Quantum-Dot Structures Hybridized with Organic Molecules

DEFF Research Database (Denmark)

Chen, Miaoxiang Max; Kobashi, K.; Chen, B.

2010-01-01

Low-dimensional III-V semiconductors have many advantages over other semiconductors; however, they are not particularly stable under physiological conditions. Hybridizing biocompatible organic molecules with advanced optical and electronic semiconductor devices based on quantum dots (QDs...

Dynamic Control of Synaptic Adhesion and Organizing Molecules in Synaptic Plasticity

Energy Technology Data Exchange (ETDEWEB)

Rudenko, Gabby (Texas-MED)

2017-01-01

Synapses play a critical role in establishing and maintaining neural circuits, permitting targeted information transfer throughout the brain. A large portfolio of synaptic adhesion/organizing molecules (SAMs) exists in the mammalian brain involved in synapse development and maintenance. SAMs bind protein partners, formingtrans-complexes spanning the synaptic cleft orcis-complexes attached to the same synaptic membrane. SAMs play key roles in cell adhesion and in organizing protein interaction networks; they can also provide mechanisms of recognition, generate scaffolds onto which partners can dock, and likely take part in signaling processes as well. SAMs are regulated through a portfolio of different mechanisms that affect their protein levels, precise localization, stability, and the availability of their partners at synapses. Interaction of SAMs with their partners can further be strengthened or weakened through alternative splicing, competing protein partners, ectodomain shedding, or astrocytically secreted factors. Given that numerous SAMs appear altered by synaptic activity, in vivo, these molecules may be used to dynamically scale up or scale down synaptic communication. Many SAMs, including neurexins, neuroligins, cadherins, and contactins, are now implicated in neuropsychiatric and neurodevelopmental diseases, such as autism spectrum disorder, schizophrenia, and bipolar disorder and studying their molecular mechanisms holds promise for developing novel therapeutics.

Metal-organic and supramolecular architectures based on mechanically interlocked molecules

Science.gov (United States)

Fernando, Isurika Rosini

The focus of this work is on mechanically interlocked molecules (MIMs), which have unusual physicochemical and mechanical properties with potential applications in nano-scale/molecular devices and high strength materials. Rotaxanes, for example, consist of an axle-like molecule threaded through a wheel-like molecule, with bulky groups at the two ends of the axle preventing the wheel from dissociating. The position of the wheel along the axle can be switched in a controllable and reversible manner by applying external stimuli, a feature that might lead to the next generation of computers. Molecularly woven materials (MWMs), another example of molecules with mechanically interlocked features, are predicted to be unprecedentedly strong while being lightweight and flexible. With the ultimate goal of achieving control over the functioning of molecular devices in the solid state, a variety of pseudorotaxane building blocks were prepared and characterized, including a novel, rare blue-colored motif. The temperature-dependent assembly/disassembly of pseudorotaxanes was exploited for the construction of single-wavelength colorimetric temperature sensors over a 100 °C window. Pseudorotaxanes based on aromatic crown ether wheels and disubstituted 4,4'-bipyridinium axles were converted into rotaxanes upon binding to metal complexes (zinc, cadmium, mercury, copper, cobalt), and the formation of ordered crystalline arrays was studied in the solid state. The columnar organization of pseudorotaxanes by Hg2X6 2-- complexes (X = Cl, Br, I), leading to unprecedented dichroic (blue/red) rotaxane crystals, was demonstrated for the first time. From the crystal structures studied it became apparent that negatively charged metal complexes are needed for successful assembly with the positively charged pseudorotaxane units. To be able to use the more common, positively charged metal ions for rotaxane framework construction, neutral and negatively charged pseudorotaxanes were synthesized

Van Der Waals Heterostructures between Small Organic Molecules and Layered Substrates

Directory of Open Access Journals (Sweden)

Han Huang

2016-09-01

Full Text Available Two dimensional atomic crystals, like grapheme (G and molybdenum disulfide (MoS2, exhibit great interest in electronic and optoelectronic applications. The excellent physical properties, such as transparency, semiconductivity, and flexibility, make them compatible with current organic electronics. Here, we review recent progress in the understanding of the interfaces of van der Waals (vdW heterostructures between small organic molecules (pentacene, copper phthalocyanine (CuPc, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA, and dioctylbenzothienobenzothiophene (C8-BTBT and layered substrates (G, MoS2 and hexagonal boron nitride (h-BN. The influences of the underlying layered substrates on the molecular arrangement, electronic and vibrational properties will be addressed.

Effect of deuteration on the vibrational spectra of organic molecules

International Nuclear Information System (INIS)

Billes, Ferenc; Endredi, Henrietta; Varady, Balazs

2001-01-01

The stable isotope substitution of organic compounds deforms their vibrational spectra. The modifications of the spectra appear as band shifts and changes in intensities and shapes of the bands. The magnitude of the effect depends on the ratio of the masses of the new and old isotopes and on the atom active position. According to these mentioned reasons large effects can be observed only if hydrogen atoms are substituted. With the effect of the substitution we dealt already in a former lecture. In this lecture we concentrate on the effect of the change of hydrogen to deuterium. We investigate the changes both experimentally and theoretically. There are two possibilities: - the hydrogen atom is in an active position, its interaction with the environment is strong, either it can dissociate or move on the skeleton of the molecule (tautomerism, resonance) and it can build hydrogen bond, (e.g. it is connected to nitrogen and oxygen atoms); - the hydrogen atom is in an indifferent position in the molecule, its interaction with the environment is weak (e.g. it joins carbon atom). When building the hydrogen bond besides the hydrogen donors also acceptors exist, namely, oxygen and nitrogen atoms having non-bonded electron pairs. When comparing the experimental and theoretical (calculated) effects of this type of isotope changes one must take into account that the calculations refer to the isolated molecule while the experimental spectra characterize the compound. The hydrogen bond is a very strong intermolecular interaction and produces tremendous changes in the infrared spectrum of the molecule in comparison to the imagined theoretical spectrum of the molecule. Some bands disappear, appear, or shift and deform drastically. The H/D change diminishes these effects. Of course, these changes entail the shift of several bands. The Raman spectrum is less sensitive to the large dipole moment changes therefore the deuteration effect is there less dramatic. Deuteration of hydrogen

Touch sensors based on planar liquid crystal-gated-organic field-effect transistors

International Nuclear Information System (INIS)

Seo, Jooyeok; Lee, Chulyeon; Han, Hyemi; Lee, Sooyong; Nam, Sungho; Kim, Youngkyoo; Kim, Hwajeong; Lee, Joon-Hyung; Park, Soo-Young; Kang, Inn-Kyu

2014-01-01

We report a tactile touch sensor based on a planar liquid crystal-gated-organic field-effect transistor (LC-g-OFET) structure. The LC-g-OFET touch sensors were fabricated by forming the 10 μm thick LC layer (4-cyano-4 ′ -pentylbiphenyl - 5CB) on top of the 50 nm thick channel layer (poly(3-hexylthiophene) - P3HT) that is coated on the in-plane aligned drain/source/gate electrodes (indium-tin oxide - ITO). As an external physical stimulation to examine the tactile touch performance, a weak nitrogen flow (83.3 μl/s) was employed to stimulate the LC layer of the touch device. The LC-g-OFET device exhibited p-type transistor characteristics with a hole mobility of 1.5 cm 2 /Vs, but no sensing current by the nitrogen flow touch was measured at sufficiently high drain (V D ) and gate (V G ) voltages. However, a clear sensing current signal was detected at lower voltages, which was quite sensitive to the combination of V D and V G . The best voltage combination was V D = −0.2 V and V G = −1 V for the highest ratio of signal currents to base currents (i.e., signal-to-noise ratio). The change in the LC alignment upon the nitrogen flow touch was assigned as the mechanism for the present LC-g-OFET touch sensors

Lifetimes of organic photovoltaics: Design and synthesis of single oligomer molecules in order to study chemical degradation mechanisms

DEFF Research Database (Denmark)

Alstrup, J.; Norrman, K.; Jørgensen, M.

2006-01-01

Degradation mechanisms in organic and polymer photovoltaics are addressed through the study of an organic photovoltaic molecule based on a single phenylene-vinylene-type oligomer molecule. The synthesis of such a model compound with different end-groups is presented that allows for assignment...... of degradation products from different parts of the molecule. Photovoltaic devices with and without C(60) have been prepared and their characteristics under AM1.5 conditions are reported. The degradation of the active phenylene-vinylene compound in darkness and after 20h of illumination were investigated using...... a mass spectrometric technique (time-of-flight secondary ion mass spectrometry) allowing elucidation of the oxidative degradation pathways. (c) 2006 Elsevier B.V. All rights reserved....

Planar graphs theory and algorithms

CERN Document Server

Nishizeki, T

1988-01-01

Collected in this volume are most of the important theorems and algorithms currently known for planar graphs, together with constructive proofs for the theorems. Many of the algorithms are written in Pidgin PASCAL, and are the best-known ones; the complexities are linear or 0(nlogn). The first two chapters provide the foundations of graph theoretic notions and algorithmic techniques. The remaining chapters discuss the topics of planarity testing, embedding, drawing, vertex- or edge-coloring, maximum independence set, subgraph listing, planar separator theorem, Hamiltonian cycles, and single- or multicommodity flows. Suitable for a course on algorithms, graph theory, or planar graphs, the volume will also be useful for computer scientists and graph theorists at the research level. An extensive reference section is included.

"Molecules-in-Medicine": Peer-Evaluated Presentations in a Fast-Paced Organic Chemistry Course for Medical Students

Science.gov (United States)

Kadnikova, Ekaterina N.

2013-01-01

To accentuate the importance of organic chemistry in development of contemporary pharmaceuticals, a three-week unit entitled "Molecules-in-Medicine" was included in the curriculum of a comprehensive one-semester four-credit organic chemistry course. After a lecture on medicinal chemistry concepts and pharmaceutical practices, students…

The fabrication of small molecule organic light-emitting diode pixels by laser-induced forward transfer

Science.gov (United States)

Shaw-Stewart, J. R. H.; Mattle, T.; Lippert, T. K.; Nagel, M.; Nüesch, F. A.; Wokaun, A.

2013-01-01

Laser-induced forward transfer (LIFT) is a versatile organic light-emitting diode (OLED) pixel deposition process, but has hitherto been applied exclusively to polymeric materials. Here, a modified LIFT process has been used to fabricate small molecule Alq3 organic light-emitting diodes (SMOLEDs). Small molecule thin films are considerably more mechanically brittle than polymeric thin films, which posed significant challenges for LIFT of these materials. The LIFT process presented here uses a polymeric dynamic release layer, a reduced environmental pressure, and a well-defined receiver-donor gap. The Alq3 pixels demonstrate good morphology and functionality, even when compared to conventionally fabricated OLEDs. The Alq3 SMOLED pixel performances show a significant amount of fluence dependence, not observed with polymerical OLED pixels made in previous studies. A layer of tetrabutyl ammonium hydroxide has been deposited on top of the aluminium cathode, as part of the donor substrate, to improve electron injection to the Alq3, by over 600%. These results demonstrate that this variant of LIFT is applicable for the deposition of functional small molecule OLEDs as well as polymeric OLEDs.

Intercalation of organic molecules into SnS{sub 2} single crystals

Energy Technology Data Exchange (ETDEWEB)

Toh, M.L.; Tan, K.J.; Wei, F.X.; Zhang, K.K.; Jiang, H. [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Ave., Singapore 639798 (Singapore); Kloc, C., E-mail: ckloc@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Ave., Singapore 639798 (Singapore)

2013-02-15

SnS{sub 2} is a layered semiconductor with a van der Waals gap separating the covalently bonded layers. In this study, post-synthesis intercalation of donor organic amine molecules, such as ethylenediamine (en), into tin disulfide and secondary intercalation of p-phenylenediamine (PPD) and 1, 5-naphthalenediamine (NDA) into SnS{sub 2e}n have been verified with X-ray diffraction. PPD and NDA did not intercalate directly even during prolonged annealing but replaced en readily if en was already present in the van der Waals gap. The c-lattice dilation is proportional to the intercalant size. Unit cell lattices of intercalated products were determined from the positions of the X-ray diffraction peaks. Optical images taken during the intercalation showed that intercalation progressed from the periphery towards the interior of the crystal. TEM diffraction patterns in the [0 0 1] direction of SnS{sub 2} after intercalation revealed defects and stacking mismatches among the SnS{sub 2} layers caused by the intercalation. UV-Vis absorption studies showed a red shift in the band edge of the SnS{sub 2} material after intercalation. The band edge was 2.2 eV for pristine SnS{sub 2}; after intercalation with en or PPD, the absorbance spectra band edges shifted to approximately 0.7 eV or 0.5 eV, respectively. - Graphical Abstract: SnS{sub 2} single crystals were intercalated with organic amine molecules such as ethylenediamine, phenylenediamine and naphthalenediamine. Absorption studies showed red shift of band edge after intercalation, which was consistent with optical observations. X-ray diffraction indicated lattice dilation in the c-lattice of SnS{sub 2} after intercalation. Highlights: Black-Right-Pointing-Pointer Organic molecules intercalated inhomogenously between covalently bonded SnS{sub 2} layers. Black-Right-Pointing-Pointer Ethylenediamine (en) intercalate directly into SnS{sub 2}. Black-Right-Pointing-Pointer Phenylenediamine (PPD) and naphthalenediamine (NDA) can be

Investigation of Various Active Layers for Their Performance on Organic Solar Cells

Directory of Open Access Journals (Sweden)

Pao-Hsun Huang

2016-08-01

Full Text Available The theoretical mechanism of open-circuit voltages (VOC in OSCs based on various small molecule organic materials is studied. The structure under investigation is simple planar heterojunction (PHJ by thermal vacuum evaporation deposition. The various wide band gaps of small molecule organic materials are used to enhance the power conversion efficiency (PCE. The donor materials used in the device include: Alpha-sexithiophene (α-6T, Copper(II phthalocyanine (CuPc, boron subnaphthalocyanine chloride (SubNc and boron Subphthalocyanine chloride (SubPc. It is combined with fullerene or SubPc acceptor material to obtain a comprehensive understanding of the charge transport behavior. It is found that the VOC of the device is largely limited by charge transport. This was associated with the space charge effects and hole accumulation. These results are attributed to the improvement of surface roughness and work function after molybdenum trioxide (MoO3 is inserted as an anode buffer layer.

Investigation of Various Active Layers for Their Performance on Organic Solar Cells.

Science.gov (United States)

Huang, Pao-Hsun; Wang, Yeong-Her; Ke, Jhong-Ciao; Huang, Chien-Jung

2016-08-09

The theoretical mechanism of open-circuit voltages (V OC ) in OSCs based on various small molecule organic materials is studied. The structure under investigation is simple planar heterojunction (PHJ) by thermal vacuum evaporation deposition. The various wide band gaps of small molecule organic materials are used to enhance the power conversion efficiency (PCE). The donor materials used in the device include: Alpha-sexithiophene (α-6T), Copper(II) phthalocyanine (CuPc), boron subnaphthalocyanine chloride (SubNc) and boron Subphthalocyanine chloride (SubPc). It is combined with fullerene or SubPc acceptor material to obtain a comprehensive understanding of the charge transport behavior. It is found that the V OC of the device is largely limited by charge transport. This was associated with the space charge effects and hole accumulation. These results are attributed to the improvement of surface roughness and work function after molybdenum trioxide (MoO₃) is inserted as an anode buffer layer.

In vitro quantification of the performance of model-based mono-planar and bi-planar fluoroscopy for 3D joint kinematics estimation.

Science.gov (United States)

Tersi, Luca; Barré, Arnaud; Fantozzi, Silvia; Stagni, Rita

2013-03-01

Model-based mono-planar and bi-planar 3D fluoroscopy methods can quantify intact joints kinematics with performance/cost trade-off. The aim of this study was to compare the performances of mono- and bi-planar setups to a marker-based gold-standard, during dynamic phantom knee acquisitions. Absolute pose errors for in-plane parameters were lower than 0.6 mm or 0.6° for both mono- and bi-planar setups. Mono-planar setups resulted critical in quantifying the out-of-plane translation (error bi-planar in quantifying the rotation along bone longitudinal axis (error bi-planar (error comparable to bi-planar, but with halved computational costs, halved segmentation time and halved ionizing radiation dose. Bi-planar analysis better compensated for the out-of-plane uncertainty that is differently propagated to relative kinematics depending on the setup. To take its full benefits, the motion task to be investigated should be designed to maintain the joint inside the visible volume introducing constraints with respect to mono-planar analysis.

Designing small molecule polyaromatic p- and n-type semiconductor materials for organic electronics

KAUST Repository

Collis, Gavin E.

2015-12-22

By combining computational aided design with synthetic chemistry, we are able to identify core 2D polyaromatic small molecule templates with the necessary optoelectronic properties for p- and n-type materials. By judicious selection of the functional groups, we can tune the physical properties of the material making them amenable to solution and vacuum deposition. In addition to solubility, we observe that the functional group can influence the thin film molecular packing. By developing structure-property relationships (SPRs) for these families of compounds we observe that some compounds are better suited for use in organic solar cells, while others, varying only slightly in structure, are favoured in organic field effect transistor devices. We also find that the processing conditions can have a dramatic impact on molecular packing (i.e. 1D vs 2D polymorphism) and charge mobility; this has implications for material and device long term stability. We have developed small molecule p- and n-type materials for organic solar cells with efficiencies exceeding 2%. Subtle variations in the functional groups of these materials produces p- and ntype materials with mobilities higher than 0.3 cm2/Vs. We are also interested in using our SPR approach to develop materials for sensor and bioelectronic applications.

Triplet--Triplet Absorption Spectra of Organic Molecules in Condensed Phases

International Nuclear Information System (INIS)

Carmichael, I.; Hug, G.L.

1986-01-01

We present a compilation of spectral parameters associated with triplet--triplet absorption of organic molecules in condensed media. The wavelengths of maximum absorbance and the corresponding extinction coefficients, where known, have been critically evaluated. Other data, for example, lifetimes, energies and energy transfer rates, relevant to the triplet states of these molecules are included by way of comments but have not been subjected to a similar scrutiny. Work in the gas phase has been omitted, as have theoretical studies. We provide an introduction to triplet state processes in solution and solids, developing the conceptual background and offering an historical perspective on the detection and measurement of triplet state absorption. Techniques employed to populate the triplet state are reviewed and the various approaches to the estimation of the extinction coefficient of triplet--triplet absorption are critically discussed. A statistical analysis of the available data is presented and recommendations for a hierarchical choice of extinction coefficients are made. Data collection is expected to be complete through the end of 1984. Compound name, molecular formula and author indexes are appended

Investigating organic molecules responsible of auxin-like activity of humic acid fraction extracted from vermicompost

Energy Technology Data Exchange (ETDEWEB)

Scaglia, Barbara, E-mail: barbara.scaglia@unimi.it [Gruppo Ricicla Labs – DiSAA, Università degli Studi di Milano, Via Celoria 2 (Italy); Nunes, Ramom Rachide; Rezende, Maria Olímpia Oliveira [Laboratório de Química Ambiental, Universidade de São Paulo, Instituto de Química de São Carlos, Avenida Trabalhador São Carlense, 400, São Carlos (Brazil); Tambone, Fulvia [Gruppo Ricicla Labs – DiSAA, Università degli Studi di Milano, Via Celoria 2 (Italy); Adani, Fabrizio, E-mail: fabrizio.adani@unimi.it [Gruppo Ricicla Labs – DiSAA, Università degli Studi di Milano, Via Celoria 2 (Italy)

2016-08-15

This work studied the auxin-like activity of humic acids (HA) obtained from vermicomposts produced using leather wastes plus cattle dung at different maturation stages (fresh, stable and mature). Bioassays were performed by testing HA concentrations in the range of 100–6000 mg carbon L{sup −1}. {sup 13}C CPMAS-NMR and GC–MS instrumental methods were used to assess the effect of biological processes and starting organic mixtures on HA composition. Not all HAs showed IAA-like activity and in general, IAA-like activity increased with the length of the vermicomposting process. The presence of leather wastes was not necessary to produce the auxin-like activity of HA, since HA extracted from a mix of cattle manure and sawdust, where no leather waste was added, showed IAA-like activity as well. CPMAS {sup 13}CNMR revealed that HAs were similar independently of the mix used and that the humification process involved the increasing concentration of pre-existing alkali soluble fractions in the biomass. GC/MS allowed the identification of the molecules involved in IAA-like effects: carboxylic acids and amino acids. The concentration of active molecules, rather than their simple presence in HA, determined the bio-stimulating effect, and a good linear regression between auxin-like activity and active stimulating molecules concentration was found (R{sup 2} = − 0.85; p < 0.01, n = 6). - Highlights: • Vermicomposting converts waste into organic fertilizer. • Vermicomposts can have biostimulating effect for the presence of hormone-like molecules. • Auxine-like activity was associated to the vermicompost humic acid fraction (HA). • HA carboxylic acids and amino acids, were reported to act as auxin-like molecules. • A linear regression was found between molecules and auxin-like activity.

Nonlinear Transport in Organic Thin Film Transistors with Soluble Small Molecule Semiconductor.

Science.gov (United States)

Kim, Hyeok; Song, Dong-Seok; Kwon, Jin-Hyuk; Jung, Ji-Hoon; Kim, Do-Kyung; Kim, SeonMin; Kang, In Man; Park, Jonghoo; Tae, Heung-Sik; Battaglini, Nicolas; Lang, Philippe; Horowitz, Gilles; Bae, Jin-Hyuk

2016-03-01

Nonlinear transport is intensively explained through Poole-Frenkel (PF) transport mechanism in organic thin film transistors with solution-processed small molecules, which is, 6,13-bis(triisopropylsilylethynyl) (TIPS) pentacene. We outline a detailed electrical study that identifies the source to drain field dependent mobility. Devices with diverse channel lengths enable the extensive exhibition of field dependent mobility due to thermal activation of carriers among traps.

Improved fill factor in inverted planar perovskite solar cells with zirconium acetate as the hole-and-ion-blocking layer.

Science.gov (United States)

Zhang, Xuewen; Liang, Chunjun; Sun, Mengjie; Zhang, Huimin; Ji, Chao; Guo, Zebang; Xu, Yajun; Sun, Fulin; Song, Qi; He, Zhiqun

2018-03-14

Planar perovskite solar cells (PSCs) have gained great interest due to their low-temperature solution preparation and simple process. In inverted planar PSCs, an additional buffer layer is usually needed on the top of the PCBM electron-transport layer (ETL) to enhance the device performance. In this work, we used a new buffer layer, zirconium acetate (Zr(Ac) 4 ). The inclusion of the Zr(Ac) 4 buffer layer leads to the increase of FF from ∼68% to ∼79% and PCE from ∼14% to ∼17% in the planar PSCs. The UPS measurement indicates that the Zr(Ac) 4 layer has a low HOMO level of -8.2 eV, indicating that the buffer layer can act as a hole-blocking layer. Surface morphology and surface chemistry investigations reveal that the elements I, MA and Pb can diffuse across the PCBM ETL, damaging the device performance. The covering Zr(Ac) 4 molecules fill in the pinholes of the PCBM layer and effectively block the ions/molecules of the perovskite from diffusion across the ETL. The resulting more robust PCBM/Zr(Ac) 4 ETL leads to weaker ionic charge accumulation and lower diode leakage current. The double role of hole-and-ion blocking of the Zr(Ac) 4 layer explains the improved FF and PCE in the PSCs.

Vibronic coupling in ionized organic molecules: structural distortions and chemical reactions

International Nuclear Information System (INIS)

Williams, Ffrancon

2003-01-01

Ionized organic molecules (radical cations) in radiation chemistry are liable to undergo vibronic coupling whenever there is a relatively small energy gap (∼0.5-1.5 eV) between their ground and excited states. As a result of this mixing, the force constant for the symmetry-allowed vibrational mode that couples these states is lowered in the ground state of the radical cation so that deformation can take place more easily along this specific mode. This pseudo-Jahn-Teller effect can then result in a permanent structural distortion of the radical cation relative to the symmetry of the parent neutral molecule. It can also bring about an energetically favored pathway for a facile chemical rearrangement along a reaction coordinate defined by the coupling mode. Examples taken from matrix-isolation studies are used to illustrate these dramatic consequences of vibronic coupling in radical cations. Thus, the bicyclo[2.2.2]oct-2-ene and tetramethylurea radical cations are found to have twisted structures departing from the C 2v symmetry of their parent molecules, while the oxirane and bicyclo[1.1.1]pentane radical cations undergo ring-opening rearrangements along reaction coordinates that correspond to the deformational modes predicted by the pseudo-Jahn-Teller effect

Probing into hybrid organic-molecule and InAs quantum-dots nanosystem with multistacked dots-in-a-well units

DEFF Research Database (Denmark)

Chen, Miaoxiang Max; Kobashi, Kazufumi

2012-01-01

Hybridizing air-stable organic-molecules with advanced III-V semiconductor quantum-dots (QDs) structures can be utilized to create a new generation of biochemical sensing devices. In order to enhance their optical performances, the active regions in these QDs structures commonly consist of multis......Hybridizing air-stable organic-molecules with advanced III-V semiconductor quantum-dots (QDs) structures can be utilized to create a new generation of biochemical sensing devices. In order to enhance their optical performances, the active regions in these QDs structures commonly consist...

Vibrational emission analysis of the CN molecules in laser-induced breakdown spectroscopy of organic compounds

Energy Technology Data Exchange (ETDEWEB)

Fernández-Bravo, Ángel; Delgado, Tomás; Lucena, Patricia; Laserna, J. Javier, E-mail: laserna@uma.es

2013-11-01

Laser-induced breakdown spectroscopy (LIBS) of organic materials is based on the analysis of atomic and ionic emission lines and on a few molecular bands, the most important being the CN violet system and the C{sub 2} Swan system. This paper is focused in molecular emission of LIBS plasmas based on the CN (B{sup 2}Σ–X{sup 2}Σ) band, one of the strongest emissions appearing in all carbon materials when analyzed in air atmosphere. An analysis of this band with sufficient spectral resolution provides a great deal of information on the molecule, which has revealed that valuable information can be obtained from the plume chemistry and dynamics affecting the excitation mechanisms of the molecules. The vibrational emission of this molecular band has been investigated to establish the dependence of this emission on the molecular structure of the materials. The paper shows that excitation/emission phenomena of molecular species observed in the plume depend strongly on the time interval selected and on the irradiance deposited on the sample surface. Precise time resolved LIBS measurements are needed for the observation of distinctive CN emission. For the organic compounds studied, larger differences in the behavior of the vibrational emission occur at early stages after plasma ignition. Since molecular emission is generally more complex than that involving atomic emission, local plasma conditions as well as plume chemistry may induce changes in vibrational emission of molecules. As a consequence, alterations in the distribution of the emissions occur in terms of relative intensities, being sensitive to the molecular structure of every single material. - Highlights: • Vibrational emission of CN species in laser-induced plasmas has been investigated. • Distribution of vibrational emission of CN has been found to be time dependent. • Laser irradiance affects the vibrational distribution of the CN molecules. • Plume chemistry controls the excitation mechanisms of CN

Arrested Handedness and Disordered Stacking in Crystals of the Pre-helical Molecule 7,8-Dioxa[6]helicene

DEFF Research Database (Denmark)

Krebs, Frederik C; Faldt, André; Thorup, Niels

1999-01-01

A characteristic feature of many molecules of biological origin is their 'handedness' or enantiomorphism. L. Pasteur prepared and separated enantiomeric crystals in 1848.(1) Since then, manifestations of symmetry breaking have attracted much attention.(2,3) Simple models of the new horseshoe shaped...... molecule, 7,8-dioxa[6]helicene ( 1), indicated a low inversion barrier between helical enantiomers. A quasi-planar pi system capable of stack formation was also observed. The molecule in question is a so-called helicene. Aromatic helicenes and heteroaromatic helicenes constitute a class of molecules...

Theoretical Investigations Regarding Single Molecules

DEFF Research Database (Denmark)

Pedersen, Kim Georg Lind

Neoclassical Valence Bond Theory, Quantum Transport, Quantum Interference, Kondo Effect, and Electron Pumping. Trap a single organic molecule between two electrodes and apply a bias voltage across this "molecular junction". When electrons pass through the molecule, the different electron paths can...... interfere destructively or constructively. Destructive interference effects in electron transport could potentially improve thermo-electrics, organic logic circuits and energy harvesting. We have investigated destructive interference in off-resonant transport through organic molecules, and have found a set...

The cell adhesion molecule Fasciclin2 regulates brush border length and organization in Drosophila renal tubules

DEFF Research Database (Denmark)

Halberg, Kenneth Agerlin; Rainey, Stephanie M.; Veland, Iben Rønn

2016-01-01

Multicellular organisms rely on cell adhesion molecules to coordinate cell-cell interactions, and to provide navigational cues during tissue formation. In Drosophila, Fasciclin 2 (Fas2) has been intensively studied due to its role in nervous system development and maintenance; yet, Fas2 is most...... role for this well-known cell adhesion molecule, and propose that Fas2-mediated intermicrovillar homophilic adhesion complexes help stabilize the brush border....

A potentiometric titration method for the crystallization of drug-like organic molecules.

Science.gov (United States)

Du-Cuny, Lei; Huwyler, Jörg; Fischer, Holger; Kansy, Manfred

2007-09-05

It is generally accepted, that crystalline solids representing a low energy polymorph should be selected for development of oral dosage forms. As a consequence, efficient and robust procedures are needed at an early stage during drug discovery to prepare crystals from drug-like organic molecules. In contrast to the use of supersaturated solutions, we present a potentiometric crystallization procedure where saturated solutions are prepared in a controlled manner by pH-titration. Crystallization is carried out under defined conditions using the sample concentration and experimental pK(a) values as input parameters. Crystals of high quality were obtained for 11 drugs selected to demonstrate the efficiency and applicability of the new method. Technical improvements are suggested to overcome practical limitations and to enhance the possibility of obtaining crystals from molecules in their uncharged form.

Formation of highly oxygenated organic molecules from aromatic compounds

Science.gov (United States)

Molteni, Ugo; Bianchi, Federico; Klein, Felix; El Haddad, Imad; Frege, Carla; Rossi, Michel J.; Dommen, Josef; Baltensperger, Urs

2018-02-01

Anthropogenic volatile organic compounds (AVOCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Formation of highly oxygenated organic molecules from aromatic compounds

Directory of Open Access Journals (Sweden)

U. Molteni

2018-02-01

Full Text Available Anthropogenic volatile organic compounds (AVOCs often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs, such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs with an O : C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene and ethylbenzene, as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl. We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AVOCs may contribute substantially to new particle formation events that have been detected in urban areas.

Insights into the effects of solvent properties in graphene based electric double-layer capacitors with organic electrolytes

Science.gov (United States)

Zhang, Shuo; Bo, Zheng; Yang, Huachao; Yang, Jinyuan; Duan, Liangping; Yan, Jianhua; Cen, Kefa

2016-12-01

Organic electrolytes are widely used in electric double-layer capacitors (EDLCs). In this work, the microstructure of planar graphene-based EDLCs with different organic solvents are investigated with molecular dynamics simulations. Results show that an increase of solvent polarity could weaken the accumulation of counter-ions nearby the electrode surface, due to the screen of electrode charges and relatively lower ionic desolvation. It thus suggests that solvents with low polarity could be preferable to yield high EDL capacitance. Meanwhile, the significant effects of the size and structure of solvent molecules are reflected by non-electrostatic molecule-electrode interactions, further influencing the adsorption of solvent molecules on electrode surface. Compared with dimethyl carbonate, γ-butyrolactone, and propylene carbonate, acetonitrile with relatively small-size and linear structure owns weak non-electrostatic interactions, which favors the easy re-orientation of solvent molecules. Moreover, the shift of solvent orientation in surface layer, from parallel orientation to perpendicular orientation relative to the electrode surface, deciphers the solvent twin-peak behavior near negative electrode. The as-obtained insights into the roles of solvent properties on the interplays among particles and electrodes elucidate the solvent influences on the microstructure and capacitive behavior of EDLCs using organic electrolytes.

Labelled molecules, modern research implements

International Nuclear Information System (INIS)

Pichat, L.; Langourieux, Y.

1974-01-01

Details of the synthesis of carbon 14- and tritium-labelled molecules are examined. Although the methods used are those of classical organic chemistry the preparation of carbon 14-labelled molecules differs in some respects, most noticeably in the use of 14 CO 2 which requires very special handling techniques. For the tritium labelling of organic molecules the methods are somewhat different, very often involving exchange reactions. The following are described in turn: the so-called Wilzbach exchange method; exchange by catalysis in solution; catalytic hydrogenation with tritium; reductions with borotritides. Some applications of labelled molecules in organic chemistry, biochemistry and pharmacology are listed [fr

Biotin conjugated organic molecules and proteins for cancer therapy: A review.

Science.gov (United States)

Maiti, Santanu; Paira, Priyankar

2018-02-10

The main transporter for biotin is sodium dependent multivitamin transporter (SMVT), which is overexpressed in various aggressive cancer cell lines such as ovarian (OV 2008, ID8), leukemia (L1210FR), mastocytoma (P815), colon (Colo-26), breast (4T1, JC, MMT06056), renal (RENCA, RD0995), and lung (M109) cancer cell lines. Furthermore, its overexpression was found higher to that of folate receptor. Therefore, biotin demand in the rapidly growing tumors is higher than normal tissues. Several biotin conjugated organic molecules has been reported here for selective delivery of the drug in cancer cell. Biotin conjugated molecules are showing higher fold of cytotoxicity in biotin positive cancer cell lines than the normal cell. Nanoparticles and polymer surface modified drugs and biotin mediated cancer theranostic strategy was highlighted in this review. The cytotoxicity and selectivity of the drug in cancer cells has enhanced after biotin conjugation. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Cyclodextrin-supported organic matrix for application of MALDI-MS for forensics. Soft-ionization to obtain protonated molecules of low molecular weight compounds

International Nuclear Information System (INIS)

Yonezawa, Tetsu; Asano, Takashi; Fujino, Tatsuya; Nishihara, Hiroshi

2013-01-01

Highlights: ► MALDI-MS applications for drug identification in forensic science is investigated. ► Cyclodextrin-supported organic matrices strongly suppress the obstacle peaks of organic matrix compounds. ► Cyclodextrin-supported organic matrices also suppress the alkali adducted molecule peaks. ► Sugar units of cyclodextrins work for this specific features. - Abstract: A mass measurement technique for detecting low-molecular-weight drugs with a cyclodextrin-supported organic matrix was investigated. By using cyclodextrin-supported 2,4,6-trihydroxyacetophenone (THAP), the matrix-related peaks of drugs were suppressed. The peaks of protonated molecules of the sample and THAP were mainly observed, and small fragments were detected in a few cases. Despite the Na + and K + peaks were observed in the spectrum, Na + or K + adduct sample molecules were undetected, owing to the sugar units of cyclodextrin. The advantages of MALDI-MS with cyclodextrin-supported matrices as an analytical tool for forensic samples are discussed. The suppression of alkali adducted molecules and desorption process are also discussed

Syntheses of planar 1,5,2,4,6,8-dithiotetrazocine derivatives and thermodynamic study on intermolecular charge transfer for developing efficient organic solar cell

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao-Zhi, E-mail: zhangchaozhi@nuist.edu.cn [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Shen, Dan [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Yuan, Yang [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Song, Ming-Xia; Li, Shi-Juan [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Cao, Hui, E-mail: yccaoh@hotmail.com [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China)

2016-07-01

A series of planar 1,5,2,4,6,8-dithiotetrazocine derivatives were synthesized for study on charge transfer at donor/acceptor interface. The fluorescence quenching spectra, and the highest occupied molecular orbital (−6.10 ∼ −6.25 eV) and the lowest unoccupied molecular orbital (−3.45 ∼ −3.58 eV) energy levels of these 1,5,2,4,6,8-dithiotetrazocine derivatives show that they would be potential acceptor materials. Based on theoretical calculations, thermodynamic study on charge transfer at donor/acceptor interface was carried out. The results of experiments and theoretical calculations show that the electrons could transfer spontaneously from poly(3-hexylthiophene) to these acceptors. The percentages of fluorescence quenching increase with negative Gibbs free energy values increasing in the charge transfer procedures. Therefore, short circuit current values of organic solar cells would increase with the Gibbs free energy values increasing. This paper suggests a useful way for developing efficient organic solar cells. - Highlights: • Syntheses of planar 1,5,2,4,6,8-dithiotetrazocine derivatives for develop effective acceptor. • Electrons at excited state in P3HT could transfer spontaneously to these acceptors. • Thermodynamic study on charge transfer at donor/acceptor interface. • Short circuit currents would be predicted by Gibbs free energy in procedure of charge transfer.

Matrix effect on hydrogen-atom tunneling of organic molecules in cryogenic solids

International Nuclear Information System (INIS)

Ichikawa, Tsuneki

2000-01-01

Although the tunneling of atoms through potential energy barriers separating the reactant and reaction systems is not paid much attention in organic reactions, this plays an important role in reactions including the transfer of light atoms. Atomic tunneling is especially important for chemical reactions at low temperatures, since the thermal activation of reactant systems is very slow process in comparison with the tunneling. One of the typical reactions of atomic tunneling is hydrogen-atom abstraction from alkanes in cryogenic solids exposed to high-energy radiation. Irradiation of alkane molecules causes the homolytic cleavage of C-H bonds, which results in the pairwise formation of free hydrogen atoms and organic free radicals. Since the activation energies for the abstraction of hydrogen atoms from alkane molecules by free hydrogen atoms are higher than 5 kcal/mol, the lifetime of free hydrogen atoms at 77 K is estimated from the Arrhenius equation of k=vexp(-E a /RT) to be longer than 10 hrs. However, except for solid methane, free hydrogen atoms immediately convert to alkyl radicals even at 4.2 K by hydrogen-atom tunneling from alkane molecules to the free hydrogen atoms. The rate of hydrogen atom tunneling does not necessary increase with decreasing activation energy or the peak height of the potential energy barrier preventing the tunneling. Although the activation energy is the lowest at the tertiary carbon of alkanes, hydrogen atom tunneling from branched alkanes with tertiary carbon at the antepenultimate position of the carbon skeleton is the fastest at the secondary penultimate carbon. Based on our experimental results, we have proposed that the peculiarity of the hydrogen-atom abstraction in cryogenic solids comes from the steric hindrance by matrix molecules to the deformation of alkane molecules from the initial sp 3 to the final sp 2 configurations. The steric hindrance causes the increase of the height of the potential energy barrier for the

Recent advances in graphene-based planar micro-supercapacitors for on-chip energy storage

Institute of Scientific and Technical Information of China (English)

Zhong-Shuai Wu; Xinliang Feng; Hui-Ming Cheng

2014-01-01

The current development trend towards miniaturized portable electronic devices has signiicantly increased the demand for ultrathin, lexible and sustainable on-chip micro-supercapacitors that have enormous potential to complement, or even to replace, micro-bateries and electrolytic capacitors. In this regard,graphene-based micro-supercapacitors with a planar geometry are promising micro-electrochemical energy-storage devices that can take full advantage of planar coniguration and unique features of graphene.his review summarizes the latest advances in on-chip graphene-based planar interdigital micro-supercapacitors, from the history of their development, representative graphene-based materials(graphene sheets, graphene quantum dots and graphene hybrids) for their manufacture, typical microfabrication strategies(photolithography techniques, electrochemical methods, laser writing, etc.),electrolyte(aqueous, organic, ionic and gel), to device coniguration(symmetric and asymmetric). Finally,the perspectives and possible development directions of future graphene-based micro-supercapacitors are briely discussed.

Employing exciton transfer molecules to increase the lifetime of phosphorescent red organic light emitting diodes

Science.gov (United States)

Lindla, Florian; Boesing, Manuel; van Gemmern, Philipp; Bertram, Dietrich; Keiper, Dietmar; Heuken, Michael; Kalisch, Holger; Jansen, Rolf H.

2011-04-01

The lifetime of phosphorescent red organic light emitting diodes (OLEDs) is investigated employing either N,N'-diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine (NPB), TMM117, or 4,4',4″-tris(N-carbazolyl)-triphenylamine (TCTA) as hole-conducting host material (mixed with an electron conductor). All OLED (organic vapor phase deposition-processed) show similar efficiencies around 30 lm/W but strongly different lifetimes. Quickly degrading OLED based on TCTA can be stabilized by doping exciton transfer molecules [tris-(phenyl-pyridyl)-Ir (Ir(ppy)3)] to the emission layer. At a current density of 50 mA/cm2 (12 800 cd/m2), a lifetime of 387 h can be achieved. Employing exciton transfer molecules is suggested to prevent the degradation of the red emission layer in phosphorescent white OLED.

On the nucleation and initial film growth of rod-like organic molecules

Science.gov (United States)

Winkler, Adolf

2016-10-01

In this article, some fundamental topics related to the initial steps of organic film growth are reviewed. General conclusions will be drawn based on experimental results obtained for the film formation of oligophenylene and pentacene molecules on gold and mica substrates. Thin films were prepared via physical vapor deposition under ultrahigh-vacuum conditions and characterized in-situ mainly by thermal desorption spectroscopy, and ex-situ by X-ray diffraction and atomic force microscopy. In this short review article the following topics will be discussed: What are the necessary conditions to form island-like films which are either composed of flat-lying or of standing molecules? Does a wetting layer exist below and in between the islands? What is the reason behind the occasionally observed bimodal island size distribution? Can one describe the nucleation process with the diffusion-limited aggregation model? Do the impinging molecules directly adsorb on the surface or rather via a hot-precursor state? Finally, it will be described how the critical island size can be determined by an independent measurement of the deposition rate dependence of the island density and the capture-zone distribution via a universal relationship.

Carbon-13 nuclear magnetic resonance of strained organic molecules: III estimates of steric effects

International Nuclear Information System (INIS)

Seidl, P.R.; Leal, K.Z.; Costa, V.E.U.; Rio Grande do Sul Univ., Porto Alegre

1985-01-01

A study of cyclic organic molecules using carbon-13 NMR spectroscopy is analysed. The preparation of compounds and the use of norbornyl compounds as a basis for chemical shifts, bicyclic, tricyclic and tetracyclic derivatives are compared. Relevant distances, angles and non-bonded interactions are shown. (M.J.C.) [pt

Diffusion as a function of guest molecule length and functionalization in flexible metal–organic frameworks

KAUST Repository

Zheng, B.; Wang, L. L.; Du, L.; Pan, Y.; Lai, Zhiping; Huang, Kuo-Wei; Du, H. L.

2016-01-01

Understanding guest diffusion in nanoporous host-guest systems is crucial in the efficient design of metal-organic frameworks (MOFs) for chemical separation and drug delivery applications. In this work, we investigated the effect of molecule length on the diffusion rate in the zeolitic imidazolate framework 8 (ZIF-8), trying to find a simple and straightforward variable to characterize the complicated guest diffusion. We found that, counter-intuitively, long guest molecules can diffuse as quickly as short molecules; the diffusion coefficient of ethyl acetate for example is of the same order of magnitude as ethane and ethanol, as excludes the existence of a simple relationship between molecule length and diffusion rate. This phenomenon is explained by a study of the contributions of intra- and inter-cage movement to overall transport. Steric confinement limits the degrees of freedom of long guest molecules, shortening their residence time and increasing the efficiency of radial diffusion. In contrast, shorter molecules meander within MOF cages, reducing transport. Furthermore, the energy barrier of inter-cage transport also does not exhibit a simple dependence on a guest molecule length, attributing to the effect of the type of functional group on diffusion. Guests over varying lengths were investigated by using theoretical methods, revealing that the guest diffusion in ZIF-8 depends on the number of contiguous carbon atoms in a molecule, rather than its overall length. Thus, we proposed simple criteria to predict arbitrary guest molecule diffusivity in ZIF-8 without time-consuming experimentation. © 2016 The Royal Society of Chemistry.

Diffusion as a function of guest molecule length and functionalization in flexible metal–organic frameworks

KAUST Repository

Zheng, B.

2016-05-11

Understanding guest diffusion in nanoporous host-guest systems is crucial in the efficient design of metal-organic frameworks (MOFs) for chemical separation and drug delivery applications. In this work, we investigated the effect of molecule length on the diffusion rate in the zeolitic imidazolate framework 8 (ZIF-8), trying to find a simple and straightforward variable to characterize the complicated guest diffusion. We found that, counter-intuitively, long guest molecules can diffuse as quickly as short molecules; the diffusion coefficient of ethyl acetate for example is of the same order of magnitude as ethane and ethanol, as excludes the existence of a simple relationship between molecule length and diffusion rate. This phenomenon is explained by a study of the contributions of intra- and inter-cage movement to overall transport. Steric confinement limits the degrees of freedom of long guest molecules, shortening their residence time and increasing the efficiency of radial diffusion. In contrast, shorter molecules meander within MOF cages, reducing transport. Furthermore, the energy barrier of inter-cage transport also does not exhibit a simple dependence on a guest molecule length, attributing to the effect of the type of functional group on diffusion. Guests over varying lengths were investigated by using theoretical methods, revealing that the guest diffusion in ZIF-8 depends on the number of contiguous carbon atoms in a molecule, rather than its overall length. Thus, we proposed simple criteria to predict arbitrary guest molecule diffusivity in ZIF-8 without time-consuming experimentation. © 2016 The Royal Society of Chemistry.

Modeling the planar configuration of extraordinary magnetoresistance

International Nuclear Information System (INIS)

El-Ahmar, S; Pozniak, A A

2015-01-01

Recently the planar version of the extraordinary magnetoresistance (EMR) magnetic field sensor has been constructed and verified in practice. Planar configuration of the EMR device gives many technological advantages, it is simpler than the classic and allows one to build the sensor using electric materials of the new type (such as graphene or topological insulators) much easier. In this work the planar configuration of the EMR sensor is investigated by performing computational simulations using the finite element method (FEM). The computational comparison of the planar and classic configurations of EMR is presented using three-dimensional models. Various variants of the geometry of EMR sensor components are pondered and compared in the planar and classic version. Size of the metal overlap is considered for sensor optimization as well as various semiconductor-metal contact resistance dependences of the EMR signal. Based on computational simulations, a method for optimal placement of electric terminals in a planar EMR device is proposed. (paper)

Manipulating the dipole layer of polar organic molecules on metal surfaces via different charge-transfer channels

Science.gov (United States)

Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Wang, Chin-Yung; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

The key properties of organic films such as energy level alignment (ELA), work functions, and injection barriers are closely linked to this dipole layer. Using angle resolved photoemission spectroscopy (ARPES), we systemically investigate the coverage-dependent work functions and spectra line shapes of occupied molecular orbital states of a polar molecule, chloroaluminium phthalocyanine (ClAlPc), grown on Ag(111) to show that the orientations of the first ClAlPc layer can be manipulated via the molecule deposition rate and post annealing, causing ELA at organic-metal interface to differ for about 0.3 eV between Cl-up and Cl-down configuration. Moreover, by comparing the experimental results with the calculations based on both gas-phase model and realistic model of ClAlPc on Ag(111) , we evidence that the different orientations of ClAlPc dipole layers lead to different charge-transfer channels between ClAlPc and Ag, a key factor that controls the ELA at organic-metal interface.

Contracting a planar graph efficiently

DEFF Research Database (Denmark)

Holm, Jacob; Italiano, Giuseppe F.; Karczmarz, Adam

2017-01-01

the data structure, we can achieve optimal running times for decremental bridge detection, 2-edge connectivity, maximal 3-edge connected components, and the problem of finding a unique perfect matching for a static planar graph. Furthermore, we improve the running times of algorithms for several planar...

Intracellular delivery of peptide nucleic acid and organic molecules using zeolite-L nanocrystals.

Science.gov (United States)

Bertucci, Alessandro; Lülf, Henning; Septiadi, Dedy; Manicardi, Alex; Corradini, Roberto; De Cola, Luisa

2014-11-01

The design and synthesis of smart nanomaterials can provide interesting potential applications for biomedical purposes from bioimaging to drug delivery. Manufacturing multifunctional systems in a way to carry bioactive molecules, like peptide nucleic acids able to recognize specific targets in living cells, represents an achievement towards the development of highly selective tools for both diagnosis and therapeutics. This work describes a very first example of the use of zeolite nanocrystals as multifunctional nanocarriers to deliver simultaneously PNA and organic molecules into living cells. Zeolite-L nanocrystals are functionalized by covalently attaching the PNA probes onto the surface, while the channel system is filled with fluorescent guest molecules. The cellular uptake of the PNA/Zeolite-L hybrid material is then significantly increased by coating the whole system with a thin layer of biodegradable poly-L-lysine. The delivery of DAPI as a model drug molecule, inserted into the zeolite pores, is also demonstrated to occur in the cells, proving the multifunctional ability of the system. Using this zeolite nanosystem carrying PNA probes designed to target specific RNA sequences of interest in living cells could open new possibilities for theranostic and gene therapy applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inkjet-based adaptive planarization (Conference Presentation)

Science.gov (United States)

Singhal, Shrawan; Grigas, Michelle M.; Khusnatdinov, Niyaz; Sreenivasan, Srinivasan V.

2017-03-01

Planarization is a critical unit step in the lithography process because it enables patterning of surfaces with versatile pattern density without compromising on the stringent planarity and depth-of-focus requirements. In addition to nanoscale pattern density variation, parasitics such as pre-existing wafer topography, can corrupt the desired process output after planarization. The topography of any surface can be classified in three broad categories, depending upon the amplitude and spatial wavelength of the same [1], [2]: (i) nominal shape, (ii) nanotopography and (iii) roughness. The nominal shape is given by the largest spatial wavelengths, typically back is one technique used for micron scale device manufacturing [3]. As the name implies, a glass dielectric is spin-coated on the substrate followed by etching in a chemistry that ensures equal etching rates for both the sacrificial glass and the underlying film or substrate material. Photoresists may also be used instead of glass. However, the global planarity that can be achieved by this technique is limited. Also, planarization over a large isolated topographical feature has been studied for the reverse-tone Jet-and-Flash Imprint Lithography process, also known as JFIL-R [4]. This relies on surface tension and capillary effects to smoothen a spin-coated Si containing film that can be etched to obtain a smooth profile. To meet the stringent requirement of planarity in submicron device technologies Chemical Mechanical Planarization (CMP) is the most widely used planarization technology [5], [6]. It uses a combination of abrasive laden chemical slurry and a mechanical pad for achieving planar profiles. The biggest concern with CMP is the dependence of material removal rate on the pattern density of material, leading to the formation of a step between the high density and low-density. The step shows up as a long-range thickness variation in the planarized film, similar in scale to pre-existing substrate topography

Partition Coefficients of Organic Molecules in Squalane and Water/Ethanol Mixtures by Molecular Dynamics Simulations

DEFF Research Database (Denmark)

Lundsgaard, Rasmus; Kontogeorgis, Georgios; Economou, Ioannis G.

2011-01-01

coefficient can be estimated for both a small hydrophilic and a hydrophobic organic molecules between squalane (used here to mimic low density poly ethylene) and water/ethanol solutes using thermodynamic integration to calculate the free energy of solvation. Molecular dynamics simulations are performed, using...... the GROMACS software, by slowly decoupling of firstly the electrostatic and then the Lennard–Jones interactions between molecules in the simulation box. These calculations depend very much on the choice of force field. Two force fields have been tested in this work, the TraPPE-UA (united-atom) and the OPLS...

Hyperthermal surface ionization mass spectrometry of organic molecules: monoterpenes

International Nuclear Information System (INIS)

Kishi, Hiroshi; Fujii, Toshihiro.

1997-01-01

This paper describes an experimental study on the influence of kinetic energy of fast monoterpene molecules on the surface ionization efficiency and on the mass spectral patterns, using rhenium oxide (ReO 2 ) surface. Molecular kinetic energy, given to the molecules through the acceleration in the seeded supersonic molecular beam, ranged from 1 to 10 eV. Hyperthermal surface ionization mass spectra (HSIMS) were taken for various incident kinetic energies and surface temperatures. The observed mass spectra were interpreted in a purely empirical way, by means of evidence from the previous investigations, and they were compared with conventional EI techniques and with the thermal energy surface ionization technique (SIOMS; Surface Ionization Organic Mass Spectrometry). Ionization efficiency (β) was also studied. Under hyperthermal surface ionization (HSI) conditions, many kinds of fragment ions, including quite abundant odd electron ions (OE +· ) are observed. HSIMS patterns of monoterpenes are different among 6-isomers, contrary to those of SIOMS and EIMS, where very similar patterns for isomers are observed. HSIMS patterns are strongly dependent on the molecular kinetic energies. The surface temperature does not affect much the spectral patterns, but it controls the total amount of ion formation. We conclude from these mass spectral findings, HSI-mechanism contains an impulsive process of ion formation, followed by the fragmentation process as a results of the internal energies acquired through the collision processes. (author)

Tuning crystal polymorphs of a Π-extended tetrathiafulvalene-based cruciform molecule towards high-performance organic field-effect transistors

DEFF Research Database (Denmark)

Feng, Linlin; Dong, Huanli; Li, Qingyuan

2017-01-01

It is a common phenomenon for organic semiconductors to crystallize in two or more polymorphs, leading to various molecular packings and different charge transport properties. Therefore, it is a crucial issue of tuning molecular crystal polymorphs (i.e., adjusting the same molecule with different......)-based cruciform molecule, named as IF-TTF. The charge carrier mobility of the α-phase IF-TTF crystals was more than one order of magnitude higher than that of β-phase crystals, suggesting the importance of reasonably tuning molecular packing in solid state for the improvement of charge transport in organic...... semiconductors...

Tunable far infrared laser spectroscopy of Van der Waals molecules in a planar supersonic jet expansion

International Nuclear Information System (INIS)

Busarow, K.L.

1990-12-01

The gas phase high resolution spectroscopic study of weakly bound clusters can provide the information necessary to develop an intermolecular potential energy surface. This surface can then be used to better understand condensed phases. In this work, a tunable far infrared laser spectrometer is used to study weakly bound dimers produced in the newly developed continuous planar supersonic jet expansion apparatus. The water dimer is an extensively studied hydrogen bonded dimer. It undergoes several tunneling motions which result in splittings and perturbations of the rovibrational energy levels. A review is presented of much of the experimental and theoretical work done on water dimer, including a description of the combined fit of all the high resolution spectroscopic results by Coudert and Hougen. Also included is a discussion of the measurement of the K = 1 lower → K = 2 lower band performed using the tunable far infrared laser/planar jet apparatus. The preliminary results from the study of CH 4 ·H 2 O will also be presented. CH 4 ·H 2 O is unique in that unlike a strongly anisotropic complex, such as the water dimer, the monomer subunits are nearly free internal rotors. Seven bands are observed which have very similar band origins and rotational constants. Two energy level diagrams are proposed which are strongly influenced by earlier ArH 2 O studies. A brief qualitative discussion of the CH 4 ·H 2 O binding energy compared to that of ArH 2 O is also included. 152 refs., 54 figs., 20 tabs

Piecewise planar Möbius bands

DEFF Research Database (Denmark)

Gravesen, Jens

2005-01-01

t is shown that a closed polygon with an odd number of vertices is the median of exactly one piecewise planar cylinder and one piecewise planar Möbius band, intersecting each other orthogonally. A closed polygon with an even number of vertices is in the generic case neither the median...

Planar cell polarity proteins differentially regulate extracellular matrix organization and assembly during zebrafish gastrulation.

Science.gov (United States)

Dohn, Michael R; Mundell, Nathan A; Sawyer, Leah M; Dunlap, Julie A; Jessen, Jason R

2013-11-01

Zebrafish gastrulation cell movements occur in the context of dynamic changes in extracellular matrix (ECM) organization and require the concerted action of planar cell polarity (PCP) proteins that regulate cell elongation and mediolateral alignment. Data obtained using Xenopus laevis gastrulae have shown that integrin-fibronectin interactions underlie the formation of polarized cell protrusions necessary for PCP and have implicated PCP proteins themselves as regulators of ECM. By contrast, the relationship between establishment of PCP and ECM assembly/remodeling during zebrafish gastrulation is unclear. We previously showed that zebrafish embryos carrying a null mutation in the four-pass transmembrane PCP protein vang-like 2 (vangl2) exhibit increased matrix metalloproteinase activity and decreased immunolabeling of fibronectin. These data implicated for the first time a core PCP protein in the regulation of pericellular proteolysis of ECM substrates and raised the question of whether other zebrafish PCP proteins also impact ECM organization. In Drosophila melanogaster, the cytoplasmic PCP protein Prickle binds Van Gogh and regulates its function. Here we report that similar to vangl2, loss of zebrafish prickle1a decreases fibronectin protein levels in gastrula embryos. We further show that Prickle1a physically binds Vangl2 and regulates both the subcellular distribution and total protein level of Vangl2. These data suggest that the ability of Prickle1a to impact fibronectin organization is at least partly due to effects on Vangl2. In contrast to loss of either Vangl2 or Prickle1a function, we find that glypican4 (a Wnt co-receptor) and frizzled7 mutant gastrula embryos with disrupted non-canonical Wnt signaling exhibit the opposite phenotype, namely increased fibronectin assembly. Our data show that glypican4 mutants do not have decreased proteolysis of ECM substrates, but instead have increased cell surface cadherin protein expression and increased intercellular

Cyclodextrin-supported organic matrix for application of MALDI-MS for forensics. Soft-ionization to obtain protonated molecules of low molecular weight compounds

Energy Technology Data Exchange (ETDEWEB)

Yonezawa, Tetsu, E-mail: tetsu@eng.hokudai.ac.jp [Division of Materials Science and Engineering, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-8628 (Japan); Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Asano, Takashi [Division of Materials Science and Engineering, Faculty of Engineering, Hokkaido University, Kita 13, Nishi 8, Kita-ku, Sapporo, Hokkaido 060-8628 (Japan); Criminal Investigation Laboratory, Metropolitan Police Department, 2-1-1 Kasumigaseki, Chiyoda-ku, Tokyo 100-8929 (Japan); Fujino, Tatsuya [Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo 192-0397 (Japan); Nishihara, Hiroshi [Department of Chemistry, School of Science, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)

2013-06-20

Highlights: ► MALDI-MS applications for drug identification in forensic science is investigated. ► Cyclodextrin-supported organic matrices strongly suppress the obstacle peaks of organic matrix compounds. ► Cyclodextrin-supported organic matrices also suppress the alkali adducted molecule peaks. ► Sugar units of cyclodextrins work for this specific features. - Abstract: A mass measurement technique for detecting low-molecular-weight drugs with a cyclodextrin-supported organic matrix was investigated. By using cyclodextrin-supported 2,4,6-trihydroxyacetophenone (THAP), the matrix-related peaks of drugs were suppressed. The peaks of protonated molecules of the sample and THAP were mainly observed, and small fragments were detected in a few cases. Despite the Na{sup +} and K{sup +} peaks were observed in the spectrum, Na{sup +} or K{sup +} adduct sample molecules were undetected, owing to the sugar units of cyclodextrin. The advantages of MALDI-MS with cyclodextrin-supported matrices as an analytical tool for forensic samples are discussed. The suppression of alkali adducted molecules and desorption process are also discussed.

Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated Mars surface UV radiation conditions

Science.gov (United States)

Poch, Olivier; Dequaire, Tristan; Stalport, Fabien; Jaber, Maguy; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

2015-04-01

The search for organic carbon-containing molecules at the surface of Mars, as clues of past habitability or remnants of life, is a major scientific goal for Mars exploration. Several lines of evidence, including the detection of phyllosilicates, suggest that early Mars offered favorable conditions for long-term sustaining of water. As a consequence, we can assume that in those days, endogenous chemical processes, or even primitive life, may have produced organic matter on Mars. Moreover, exogenous delivery from small bodies or dust particles is likely to have brought fresh organic molecules to the surface of Mars up today. Organic matter is therefore expected to be present at the surface/subsurface of the planet. But the current environmental conditions at the surface - UV radiation, oxidants and energetic particles - generate physico-chemical processes that may affect organic molecules. On the other hand, on Earth, phyllosilicates are known to accumulate and preserve organic matter. But are phyllosilicates efficient at preserving organic molecules under the current environmental conditions at the surface of Mars? We have monitored the qualitative and quantitative evolutions of glycine, urea and adenine interacting with the Fe3+-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated Martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) in a laboratory simulation setup. We have tested organic-rich samples which may be representative of the evaporation of a warm little pond of liquid water having concentrated organics on Mars. For each molecule, we have observed how the nontronite influences the quantum efficiency of its photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine: their efficiencies of photodecomposition are reduced by a factor

A new microcavity design for single molecule detection

International Nuclear Information System (INIS)

Steiner, M.; Schleifenbaum, F.; Stupperich, C.; Failla, A.V.; Hartschuh, A.; Meixner, A.J.

2006-01-01

We present a new microcavity design which allows for efficient detection of single molecules by measuring the molecular fluorescence emission coupled into a resonant cavity mode. The Fabry-Perot-type microresonator consists of two silver mirrors separated by a thin polymer film doped with dye molecules in ultralow concenctration. By slightly tilting one of the mirrors different cavity lengths can be selected within the same sample. Locally, on a μm scale, the microcavity still acts as a planar Fabry-Perot resonator. Using scanning confocal fluorescence microscopy, single emitters on resonance with a single mode of the microresonator can be spatially addressed. Our microcavity is demonstrated to be well-suited for investigating the coupling mechanism between single quantum emitters and single modes of the electromagnetic field. The microcavity layout could be integrated in a lab-on-a-microchip design for ultrasensitive microfluidic analytics and can be considered as an important improvement for single photon sources based on single molecules operating at room temperature

Improved Dynamic Planar Point Location

DEFF Research Database (Denmark)

Brodal, Gerth Stølting; Arge, Lars; Georgiadis, Loukas

2006-01-01

We develop the first linear-space data structures for dynamic planar point location in general subdivisions that achieve logarithmic query time and poly-logarithmic update time.......We develop the first linear-space data structures for dynamic planar point location in general subdivisions that achieve logarithmic query time and poly-logarithmic update time....

Planar silver nanowire, carbon nanotube and PEDOT:PSS nanocomposite transparent electrodes

Science.gov (United States)

Stapleton, Andrew J.; Yambem, Soniya D.; Johns, Ashley H.; Afre, Rakesh A.; Ellis, Amanda V.; Shapter, Joe G.; Andersson, Gunther G.; Quinton, Jamie S.; Burn, Paul L.; Meredith, Paul; Lewis, David A.

2015-04-01

Highly conductive, transparent and flexible planar electrodes were fabricated using interwoven silver nanowires and single-walled carbon nanotubes (AgNW:SWCNT) in a PEDOT:PSS matrix via an epoxy transfer method from a silicon template. The planar electrodes achieved a sheet resistance of 6.6 ± 0.0 Ω/□ and an average transmission of 86% between 400 and 800 nm. A high figure of merit of 367 Ω-1 is reported for the electrodes, which is much higher than that measured for indium tin oxide and reported for other AgNW composites. The AgNW:SWCNT:PEDOT:PSS electrode was used to fabricate low temperature (annealing free) devices demonstrating their potential to function with a range of organic semiconducting polymer:fullerene bulk heterojunction blend systems.

Planar impact experiments for EOS measurements

International Nuclear Information System (INIS)

Furnish, M.D.

1993-01-01

The community concerned with the numerical modeling of groundshock produced by underground nuclear tests must have access to materials data to benchmark models of rock behavior. Historically the primary source of these data has been planar impact experiments. These experiments have involved gun, explosive and electrical launchers. Other methods of introducing planar shocks include shock driving by in-contact explosives or laser bursts. This paper briefly describes gun launcher-based planar impact methods used to characterize geological materials at Sandia National Laboratories

Effect of organic small-molecule hole injection materials on the performance of inverted organic solar cells

Science.gov (United States)

Li, Jie; Zheng, Yifan; Zheng, Ding; Yu, Junsheng

2016-07-01

In this study, the influence of small-molecule organic hole injection materials on the performance of organic solar cells (OSCs) as the hole transport layer (HTL) with an architecture of ITO/ZnO/P3HT:PC71BM/HTL/Ag has been investigated. A significant enhancement on the performance of OSCs from 1.06% to 2.63% is obtained by using N, N‧-bis(1-naphthalenyl)-N, N‧-bis-phenyl-(1, 1‧-biphenyl)-4, 4‧-diamine (NPB) HTL. Through the resistance simulation and space-charge limited current analysis, we found that NPB HTL cannot merely improve the hole mobility of the device but also form the Ohmic contact between the active layer and anode. Besides, when we apply mix HTL by depositing the NPB on the surface of molybdenum oxide, the power conversion efficiency of OSC are able to be further improved to 2.96%.

Solution-processed white organic light-emitting devices based on small-molecule materials

International Nuclear Information System (INIS)

Wang Dongdong; Wu Zhaoxin; Zhang Xinwen; Wang Dawei; Hou Xun

2010-01-01

We investigated solution-processed films of 4,4'-bis(2,2-diphenylvinyl)-1,1'-bibenyl (DPVBi) and its blends with N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD) by atomic force microscopy (AFM). The AFM result shows that the solution-processed films are pin-free and their morphology is smooth enough to be used in OLEDs. We have developed a solution-processed white organic light-emitting device (WOLEDs) based on small-molecules, in which the light-emitting layer (EML) was formed by spin-coating the solution of small-molecules on top of the solution-processed hole-transporting layer. This WOLEDs, in which the EML consists of co-host (DPVBi and TPD), the blue dopant (4,4'-bis[2-(4-(N,N-diphenylamino)phenyl)vinyl]biphenyl) and the yellow dye (5,6,11,12-tetraphenylnaphtacene), has a current efficiency of 6.0 cd/A at a practical luminance of 1000 cd/m 2 , a maximum luminance of 22500 cd/m 2 , and its color coordinates are quite stable. Our research shows a possible approach to achieve efficient and low-cost small-molecule-based WOLEDs, which avoids the complexities of the co-evaporation process of multiple dopants and host materials in vacuum depositions.

Small organic molecules modulating iodine uptake in thyroid

International Nuclear Information System (INIS)

Ambroise, Y.

2006-01-01

The thyroid gland accumulates large quantities of iodine. This uptake is needed for the production of iodinated hormones (T3 and T4). The first step in the iodine accumulation is a basolateral transport of iodide ions by the cloned 'Natrium Iodide Sym-porter' also called NIS. Using high-throughput screening techniques, we have identified a series of inhibitors of the iodide uptake in thyrocytes. These compounds are of medical significance in case of thyroid deregulation and can also offer solutions for radio-iodine detoxification in case of emergency situations (nuclear industry...). In addition, these small organic molecules can be important tools for the understanding of NIS structure and functions In parallel, we have identified and characterized a single compound capable to strongly enhance the amount of intra-cellular iodide in rat thyrocytes (FRTL5) as well as in HEK293 cells transfected with hNIS (Natrium/Iodide Sym-porter). Preliminary studies show that this effect is NIS dependant, and is induced by alternative and unknown mechanisms. Future work will consist in unraveling the mode of action of this molecule. These informations will help us not only to better understand the iodide pathways in the thyroid, but also to design more active analogues. We will use photo-labelling techniques to identify new proteins involved in the iodide transfer and retention. In addition, preliminary experiments are underway to validate our compound as an anti-cancer agent. Targeted NIS gene delivery into tumors plus radio-iodide injection leads to tumor size regression. Unfortunately, doses of radioactivity are to high for safe treatment. Our compound may lead to enhanced radio-iodide entrapment, thus necessitating lower doses of radioactivity for tumor regression. (author)

Anisotropic charge transport in large single crystals of π-conjugated organic molecules.

Science.gov (United States)

Hourani, Wael; Rahimi, Khosrow; Botiz, Ioan; Koch, Felix Peter Vinzenz; Reiter, Günter; Lienerth, Peter; Heiser, Thomas; Bubendorff, Jean-Luc; Simon, Laurent

2014-05-07

The electronic properties of organic semiconductors depend strongly on the nature of the molecules, their conjugation and conformation, their mutual distance and the orientation between adjacent molecules. Variations of intramolecular distances and conformation disturb the conjugation and perturb the delocalization of charges. As a result, the mobility considerably decreases compared to that of a covalently well-organized crystal. Here, we present electrical characterization of large single crystals made of the regioregular octamer of 3-hexyl-thiophene (3HT)8 using a conductive-atomic force microscope (C-AFM) in air. We find a large anisotropy in the conduction with charge mobility values depending on the crystallographic orientation of the single crystal. The smaller conduction is in the direction of π-π stacking (along the long axis of the single crystal) with a mobility value in the order of 10(-3) cm(2) V(-1) s(-1), and the larger one is along the molecular axis (in the direction normal to the single crystal surface) with a mobility value in the order of 0.5 cm(2) V(-1) s(-1). The measured current-voltage (I-V) curves showed that along the molecular axis, the current followed an exponential dependence corresponding to an injection mode. In the π-π stacking direction, the current exhibits a space charge limited current (SCLC) behavior, which allows us to estimate the charge carrier mobility.

Quality control on planar n-in-n pixel sensors — Recent progress of ATLAS planar pixel sensors

International Nuclear Information System (INIS)

Klingenberg, R.

2013-01-01

To extend the physics reach of the Large Hadron Collider (LHC), upgrades to the accelerator are planned which will increase the peak luminosity by a factor 5–10. To cope with the increased occupancy and radiation damage, the ATLAS experiment plans to introduce an all-silicon inner tracker with the high luminosity upgrade (HL-LHC). To investigate the suitability of pixel sensors using the proven planar technology for the upgraded tracker, the ATLAS Upgrade Planar Pixel Sensor (PPS) R and D Project was established. Main areas of research are the performance of planar pixel sensors at highest fluences, the exploration of possibilities for cost reduction to enable the instrumentation of large areas, the achievement of slim or active edges to provide low geometric inefficiencies without the need for shingling of modules and the investigation of the operation of highly irradiated sensors at low thresholds to increase the efficiency. The Insertable b-layer (IBL) is the first upgrade project within the ATLAS experiment and will employ a new detector layer consisting of silicon pixel sensors, which were improved and prototyped in the framework of the planar pixel sensor R and D project. A special focus of this paper is the status of the development and testing of planar n-in-n pixel sensors including the quality control of the on-going series production and postprocessing of sensor wafers. A high yield of produced planar sensor wafers and FE-I4 double chip sensors after first steps of post-processing including under bump metallization and dicing is observed. -- Highlights: ► Prototypes of irradiated planar n-in-n sensors have been successfully tested under laboratory conditions. ► A quality assurance programme on the series production of planar sensors for the IBL has started. ► A high yield of double chip sensors during the series production is observed which are compatible to the specifications to this detector component.

Single molecule conductance

NARCIS (Netherlands)

Willems, R.

2008-01-01

This thesis represents an excursion into the world of molecular electronics, i.e. the field of research trying to use individual (organic) molecules as electronic components; in this work various experimental methods have been explored to connect individual molecules to metallic contacts and

Limitations of superfluid helium droplets as host system revealed by electronic spectroscopy of embedded molecules

Energy Technology Data Exchange (ETDEWEB)

Premke, Tobias

2016-02-19

Superfluid helium nanodroplets serve a unique cryogenic host system ideal to prepare cold molecules and clusters. Structures as well as dynamic processes can be examined by means of high resolution spectroscopy. Dopant spectra are accompanied by helium-induced spectroscopic features which reveal information on the dopant to helium interaction. For this reason the experimental research focuses on the investigation of such helium-induced effects in order to provide new information on the microsolvation inside the droplets. Since the quantitative understanding of helium-induced spectral features is essential to interpret molecular spectra recorded in helium droplets, this study contributes further experimental details on microsolvation in superfluid helium droplets. For this purpose two contrary systems were examined by means of high resolution electronic spectroscopy. The first one, phthalocyanine (Pc), is a planar organic molecule offering a huge and planar surface to the helium atoms and thus, the non-superfluid helium solvation layer can form different structures. The second system is iodine and in contrast to Pc it is of simple molecular shape. That means that in this case different complex structures of the non-superfluid helium solvation layer and the dopant can be expected to be avoided. Thus, both molecules should show clear differences in their microsolvation behavior. In this work a detailed examination of different spectroscopic properties of phthalocyanine is given by means of fluorescence excitation and dispersed emission spectroscopy. It raises legitimate doubts about the assignment of experimentally observed signals to features predicted by the model of the microsolvation. Even though there are no experimental observations which disprove the empirical model for the solvation in helium droplets, an unambiguous assignment of the helium-induced spectroscopic structures is often not possible. In the second part of this work, the investigation of the

FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

International Nuclear Information System (INIS)

Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

2016-01-01

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude

Formation and Recondensation of Complex Organic Molecules during Protostellar Luminosity Outbursts

Science.gov (United States)

Taquet, Vianney; Wirström, Eva S.; Charnley, Steven B.

2016-04-01

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

FORMATION AND RECONDENSATION OF COMPLEX ORGANIC MOLECULES DURING PROTOSTELLAR LUMINOSITY OUTBURSTS

Energy Technology Data Exchange (ETDEWEB)

Taquet, Vianney [Leiden Observatory, Leiden University, P.O. Box 9513, 2300-RA Leiden (Netherlands); Wirström, Eva S. [Department of Earth and Space Sciences, Chalmers University of Technology, Onsala Space Observatory, SE-439 92 Onsala (Sweden); Charnley, Steven B. [Astrochemistry Laboratory and The Goddard Center for Astrobiology, Mailstop 691, NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20770 (United States)

2016-04-10

During the formation of stars, the accretion of surrounding material toward the central object is thought to undergo strong luminosity outbursts followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas-phase formation and recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas-phase chemical network forming COMs in which ammonia plays a key role. The model calculations presented here demonstrate that ion–molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas-phase reaction branching ratios. In spite of the short outburst timescales of about 100 years, abundance ratios of the considered species higher than 10% with respect to methanol are predicted during outbursts due to their low binding energies relative to water and methanol which delay their recondensation during cooling. Although the current luminosity of most embedded protostars would be too low to produce complex organics in the hot-core regions that are observable with current sub-millimetric interferometers, previous luminosity outburst events would induce the formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude.

Structural Ordering of Semiconducting Polymers and Small-Molecules for Organic Electronics

Science.gov (United States)

O'Hara, Kathryn Allison

Semiconducting polymers and small-molecules can be readily incorporated into electronic devices such as organic photovoltaics (OPVs), thermoelectrics (OTEs), organic light emitting diodes (OLEDs), and organic thin film transistors (OTFTs). Organic materials offer the advantage of being processable from solution to form flexible and lightweight thin films. The molecular design, processing, and resulting thin film morphology of semiconducting polymers drastically affect the optical and electronic properties. Charge transport within films of semiconducting polymers relies on the nanoscale organization to ensure electronic coupling through overlap of molecular orbitals and to provide continuous transport pathways. While the angstrom-scale packing details can be studied using X-ray scattering methods, an understanding of the mesoscale, or the length scale over which smaller ordered regions connect, is much harder to achieve. Grain boundaries play an important role in semiconducting polymer thin films where the average grain size is much smaller than the total distance which charges must traverse in order to reach the electrodes in a device. The majority of semiconducting polymers adopt a lamellar packing structure in which the conjugated backbones align in parallel pi-stacks separated by the alkyl side-chains. Only two directions of transport are possible--along the conjugated backbone and in the pi-stacking direction. Currently, the discussion of transport between crystallites is centered around the idea of tie-chains, or "bridging" polymer chains connecting two ordered regions. However, as molecular structures become increasingly complex with the development of new donor-acceptor copolymers, additional forms of connectivity between ordered domains should be considered. High resolution transmission electron microscopy (HRTEM) is a powerful tool for directly imaging the crystalline grain boundaries in polymer and small-molecule thin films. Recently, structures

Modification of mesoporous silica SBA-15 with different organic molecules to gain chemical sensors: a review

Directory of Open Access Journals (Sweden)

Negar Lashgari

2016-01-01

Full Text Available The recognition of the biologically and environmentally important ions is of great interest in the field of chemical sensors in recent years. The fluorescent sensors as a powerful optical analytical technique for the detection of low level of various analytes such as anions and metal cations have been progressively developed due to the simplicity, cost effective, and selectivity for monitoring specific analytes in various systems. Organic-inorganic hybrid nanomaterials have important advantages as solid chemosensors and various innovative hybrid materials modified by fluorescence molecules were recently prepared. On the other hand, the homogeneous porosity and large surface area of mesoporous silica make it a promising inorganic support. SBA-15 as a two-dimensional hexagonal mesoporous silica material with stable structure, thick walls, tunable pore size, and high specific surface area is a valuable substrate for modification with different organic chelating groups. This review highlights the fluorescent chemosensors for ionic species based on modification of the mesoporous silica SBA-15 with different organic molecules, which have been recently developed from our laboratory.

Coupling between diffusion and orientation of pentacene molecules on an organic surface.

Science.gov (United States)

Rotter, Paul; Lechner, Barbara A J; Morherr, Antonia; Chisnall, David M; Ward, David J; Jardine, Andrew P; Ellis, John; Allison, William; Eckhardt, Bruno; Witte, Gregor

2016-04-01

The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.

Nature of chalcogen hor ellipsis chalcogen contact interactions in organic donor-molecule salts

Energy Technology Data Exchange (ETDEWEB)

Novoa, J.J.; Whangbo, Myung-Hwan (North Carolina State Univ., Raleigh, NC (USA). Dept. of Chemistry); Williams, J.M. (Argonne National Lab., IL (USA))

1990-01-01

The nature of chalcogen{hor ellipsis}chalcogen contact interactions in organic donor-molecule salts was examined by performing ab initio SCF-MO/MP2 calculations on H{sub 2}X{hor ellipsis}XH{sub 2}(X = O, S, SE, Te) and MM2 calculations on donor dimers (TXF){sub 2} (X = S, SE, Te) and (BEDX-TTF){sub 2} (X = O, S). 14 refs., 4 figs., 4 tabs.

Blending crystalline/liquid crystalline small molecule semiconductors: A strategy towards high performance organic thin film transistors

Science.gov (United States)

He, Chao; He, Yaowu; Li, Aiyuan; Zhang, Dongwei; Meng, Hong

2016-10-01

Solution processed small molecule polycrystalline thin films often suffer from the problems of inhomogeneity and discontinuity. Here, we describe a strategy to solve these problems through deposition of the active layer from a blended solution of crystalline (2-phenyl[1]benzothieno[3,2-b][1]benzothiophene, Ph-BTBT) and liquid crystalline (2-(4-dodecylphenyl) [1]benzothieno[3,2-b]benzothiophene, C12-Ph-BTBT) small molecule semiconductors with the hot spin-coating method. Organic thin film transistors with average hole mobility approaching 1 cm2/V s, much higher than that of single component devices, have been demonstrated, mainly due to the improved uniformity, continuity, crystallinity, and stronger intermolecular π-π stacking in blend thin films. Our results indicate that the crystalline/liquid crystalline semiconductor blend method is an effective way to enhance the performance of organic transistors.

Directional cell migration establishes the axes of planar polarity in the posterior lateral-line organ of the zebrafish.

Science.gov (United States)

López-Schier, Hernán; Starr, Catherine J; Kappler, James A; Kollmar, Richard; Hudspeth, A J

2004-09-01

The proper orientation of mechanosensory hair cells along the lateral-line organ of a fish or amphibian is essential for the animal's ability to sense directional water movements. Within the sensory epithelium, hair cells are polarized in a stereotyped manner, but the mechanisms that control their alignment relative to the body axes are unknown. We have found, however, that neuromasts can be oriented either parallel or perpendicular to the anteroposterior body axis. By characterizing the strauss mutant zebrafish line and by tracking labeled cells, we have demonstrated that neuromasts of these two orientations originate from, respectively, the first and second primordia. Furthermore, altering the migratory pathway of a primordium reorients a neuromast's axis of planar polarity. We propose that the global orientation of hair cells relative to the body axes is established through an interaction between directional movement by primordial cells and the timing of neuromast maturation.

Fgf8-related secondary organizers exert different polarizing planar instructions along the mouse anterior neural tube.

Science.gov (United States)

Crespo-Enriquez, Ivan; Partanen, Juha; Martinez, Salvador; Echevarria, Diego

2012-01-01

Early brain patterning depends on proper arrangement of positional information. This information is given by gradients of secreted signaling molecules (morphogens) detected by individual cells within the responding tissue, leading to specific fate decisions. Here we report that the morphogen FGF8 exerts initially a differential signal activity along the E9.5 mouse neural tube. We demonstrate that this polarizing activity codes by RAS-regulated ERK1/2 signaling and depends on the topographical location of the secondary organizers: the isthmic organizer (IsO) and the anterior neural ridge (anr) but not on zona limitans intrathalamica (zli). Our results suggest that Sprouty2, a negative modulator of RAS/ERK pathway, is important for regulating Fgf8 morphogenetic signal activity by controlling Fgf8-induced signaling pathways and positional information during early brain development.

Ambipolar Small-Molecule:Polymer Blend Semiconductors for Solution-Processable Organic Field-Effect Transistors.

Science.gov (United States)

Kang, Minji; Hwang, Hansu; Park, Won-Tae; Khim, Dongyoon; Yeo, Jun-Seok; Kim, Yunseul; Kim, Yeon-Ju; Noh, Yong-Young; Kim, Dong-Yu

2017-01-25

We report on the fabrication of an organic thin-film semiconductor formed using a blend solution of soluble ambipolar small molecules and an insulating polymer binder that exhibits vertical phase separation and uniform film formation. The semiconductor thin films are produced in a single step from a mixture containing a small molecular semiconductor, namely, quinoidal biselenophene (QBS), and a binder polymer, namely, poly(2-vinylnaphthalene) (PVN). Organic field-effect transistors (OFETs) based on QBS/PVN blend semiconductor are then assembled using top-gate/bottom-contact device configuration, which achieve almost four times higher mobility than the neat QBS semiconductor. Depth profile via secondary ion mass spectrometry and atomic force microscopy images indicate that the QBS domains in the films made from the blend are evenly distributed with a smooth morphology at the bottom of the PVN layer. Bias stress test and variable-temperature measurements on QBS-based OFETs reveal that the QBS/PVN blend semiconductor remarkably reduces the number of trap sites at the gate dielectric/semiconductor interface and the activation energy in the transistor channel. This work provides a one-step solution processing technique, which makes use of soluble ambipolar small molecules to form a thin-film semiconductor for application in high-performance OFETs.

Modified planar functions and their components

DEFF Research Database (Denmark)

Anbar Meidl, Nurdagül; Meidl, Wilfried Meidl

2017-01-01

functions in odd characteristic as a vectorial bent function. We finally point out that though these components behave somewhat different than the multivariate bent4 functions, they are bent or semibent functions shifted by a certain quadratic term, a property which they share with their multivariate......Zhou ([20]) introduced modified planar functions in order to describe (2n; 2n; 2n; 1) relative difference sets R as a graph of a function on the finite field F2n, and pointed out that projections of R are difference sets that can be described by negabent or bent4 functions, which are Boolean...... functions given in multivariate form. One of the objectives of this paper is to contribute to the understanding of these component functions of modified planar functions. Moreover, we obtain a description of modified planar functions by their components which is similar to that of the classical planar...

Benchmarking density functional tight binding models for barrier heights and reaction energetics of organic molecules.

Science.gov (United States)

Gruden, Maja; Andjeklović, Ljubica; Jissy, Akkarapattiakal Kuriappan; Stepanović, Stepan; Zlatar, Matija; Cui, Qiang; Elstner, Marcus

2017-09-30

Density Functional Tight Binding (DFTB) models are two to three orders of magnitude faster than ab initio and Density Functional Theory (DFT) methods and therefore are particularly attractive in applications to large molecules and condensed phase systems. To establish the applicability of DFTB models to general chemical reactions, we conduct benchmark calculations for barrier heights and reaction energetics of organic molecules using existing databases and several new ones compiled in this study. Structures for the transition states and stable species have been fully optimized at the DFTB level, making it possible to characterize the reliability of DFTB models in a more thorough fashion compared to conducting single point energy calculations as done in previous benchmark studies. The encouraging results for the diverse sets of reactions studied here suggest that DFTB models, especially the most recent third-order version (DFTB3/3OB augmented with dispersion correction), in most cases provide satisfactory description of organic chemical reactions with accuracy almost comparable to popular DFT methods with large basis sets, although larger errors are also seen for certain cases. Therefore, DFTB models can be effective for mechanistic analysis (e.g., transition state search) of large (bio)molecules, especially when coupled with single point energy calculations at higher levels of theory. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Orientifold Planar Equivalence: The Chiral Condensate

DEFF Research Database (Denmark)

Armoni, Adi; Lucini, Biagio; Patella, Agostino

2008-01-01

The recently introduced orientifold planar equivalence is a promising tool for solving non-perturbative problems in QCD. One of the predictions of orientifold planar equivalence is that the chiral condensates of a theory with $N_f$ flavours of Dirac fermions in the symmetric (or antisymmetric...

Overview of Planar Magnetic Technology — Fundamental Properties

DEFF Research Database (Denmark)

Ouyang, Ziwei; Andersen, Michael A. E.

2014-01-01

The momentum towards high efficiency, high frequency, and high power density in power supplies limits wide use of conventional wire-wound magnetic components. This article gives an overview of planar magnetic technologies with respect to the development of modern power electronics. The major...... advantages and disadvantages in the use of planar magnetics for high frequency power converters are covered, and publications on planar magnetics are reviewed. A detailed survey of winding conduction loss, leakage inductance and winding capacitance for planar magnetics is presented so power electronics...

Sol-gel method for encapsulating molecules

Science.gov (United States)

Brinker, C. Jeffrey; Ashley, Carol S.; Bhatia, Rimple; Singh, Anup K.

2002-01-01

A method for encapsulating organic molecules, and in particular, biomolecules using sol-gel chemistry. A silica sol is prepared from an aqueous alkali metal silicate solution, such as a mixture of silicon dioxide and sodium or potassium oxide in water. The pH is adjusted to a suitably low value to stabilize the sol by minimizing the rate of siloxane condensation, thereby allowing storage stability of the sol prior to gelation. The organic molecules, generally in solution, is then added with the organic molecules being encapsulated in the sol matrix. After aging, either a thin film can be prepared or a gel can be formed with the encapsulated molecules. Depending upon the acid used, pH, and other processing conditions, the gelation time can be from one minute up to several days. In the method of the present invention, no alcohols are generated as by-products during the sol-gel and encapsulation steps. The organic molecules can be added at any desired pH value, where the pH value is generally chosen to achieve the desired reactivity of the organic molecules. The method of the present invention thereby presents a sufficiently mild encapsulation method to retain a significant portion of the activity of the biomolecules, compared with the activity of the biomolecules in free solution.

Film formation of non-planar phthalocyanines on copper(i) iodide

OpenAIRE

Ramadan, A. J.; Fearn, S.; Jones, T. S. (Tim S.); Heutz, S.; Rochford, L. A. (Luke A.)

2016-01-01

Structural templating is frequently used in organic photovoltaic devices to control the properties of the functional layers and therefore improve efficiencies. Modification of the substrate temperatures has also been shown to impact the structure and morphology of phthalocyanine thin films. Here we combine templating by copper iodide and high substrate temperature growth and study its effect on the structure and morphology of two different non-planar phthalocyanines, chloroaluminium (ClAlPc) ...

Intracellular Delivery of a Planar DNA Origami Structure by the Transferrin-Receptor Internalization Pathway

DEFF Research Database (Denmark)

Schaffert, David Henning; Okholm, Anders Hauge; Sørensen, Rasmus Schøler

2016-01-01

DNA origami provides rapid access to easily functionalized, nanometer-sized structures making it an intriguing platform for the development of defined drug delivery and sensor systems. Low cellular uptake of DNA nanostructures is a major obstacle in the development of DNA-based delivery platforms....... Herein, significant strong increase in cellular uptake in an established cancer cell line by modifying a planar DNA origami structure with the iron transport protein transferrin (Tf) is demonstrated. A variable number of Tf molecules are coupled to the origami structure using a DNA-directed, site...... on the origami surface....

Chirality in distorted square planar Pd(O,N)2 compounds.

Science.gov (United States)

Brunner, Henri; Bodensteiner, Michael; Tsuno, Takashi

2013-10-01

Salicylidenimine palladium(II) complexes trans-Pd(O,N)2 adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N-substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)2 unit. In complexes with enantiomerically pure N-substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)2 complexes with bridging N-substituents in trans-arrangement are inherently chiral. For dimers different chirality patterns for the Pd(O,N)2 square are observed. The crystals contain racemates of enantiomers. In complex two independent molecules form a tight pair. The (RC) configuration of the ligand induces the same Δ chirality in the Pd(O,N)2 units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes and atrop isomerism induces specific configurations in the Pd(O,N)2 bowl systems. The square chirality is largest for complex [(Diop)Rh(PPh3 )Cl)], a catalyst for enantioselective hydrogenation. In the lattice of two diastereomers with the same (RC ,RC) configuration in the ligand Diop but opposite Δ and Λ square configurations co-crystallize, a rare phenomenon in stereochemistry. © 2013 Wiley Periodicals, Inc.

Stereoscopic Planar Laser-Induced Fluorescence Imaging at 500 kHz

Science.gov (United States)

Medford, Taylor L.; Danehy, Paul M.; Jones, Stephen B.; Jiang, N.; Webster, M.; Lempert, Walter; Miller, J.; Meyer, T.

2011-01-01

A new measurement technique for obtaining time- and spatially-resolved image sequences in hypersonic flows is developed. Nitric-oxide planar laser-induced fluorescence (NO PLIF) has previously been used to investigate transition from laminar to turbulent flow in hypersonic boundary layers using both planar and volumetric imaging capabilities. Low flow rates of NO were typically seeded into the flow, minimally perturbing the flow. The volumetric imaging was performed at a measurement rate of 10 Hz using a thick planar laser sheet that excited NO fluorescence. The fluorescence was captured by a pair of cameras having slightly different views of the flow. Subsequent stereoscopic reconstruction of these images allowed the three-dimensional flow structures to be viewed. In the current paper, this approach has been extended to 50,000 times higher repetition rates. A laser operating at 500 kHz excites the seeded NO molecules, and a camera, synchronized with the laser and fitted with a beam-splitting assembly, acquires two separate images of the flow. The resulting stereoscopic images provide three-dimensional flow visualizations at 500 kHz for the first time. The 200 ns exposure time in each frame is fast enough to freeze the flow while the 500 kHz repetition rate is fast enough to time-resolve changes in the flow being studied. This method is applied to visualize the evolving hypersonic flow structures that propagate downstream of a discrete protuberance attached to a flat plate. The technique was demonstrated in the NASA Langley Research Center s 31-Inch Mach 10 Air Tunnel facility. Different tunnel Reynolds number conditions, NO flow rates and two different cylindrical protuberance heights were investigated. The location of the onset of flow unsteadiness, an indicator of transition, was observed to move downstream during the tunnel runs, coinciding with an increase in the model temperature.

Visualizing electron dynamics in organic materials: Charge transport through molecules and angular resolved photoemission

Science.gov (United States)

Kümmel, Stephan

Being able to visualize the dynamics of electrons in organic materials is a fascinating perspective. Simulations based on time-dependent density functional theory allow to realize this hope, as they visualize the flow of charge through molecular structures in real-space and real-time. We here present results on two fundamental processes: Photoemission from organic semiconductor molecules and charge transport through molecular structures. In the first part we demonstrate that angular resolved photoemission intensities - from both theory and experiment - can often be interpreted as a visualization of molecular orbitals. However, counter-intuitive quantum-mechanical electron dynamics such as emission perpendicular to the direction of the electrical field can substantially alter the picture, adding surprising features to the molecular orbital interpretation. In a second study we calculate the flow of charge through conjugated molecules. The calculations show in real time how breaks in the conjugation can lead to a local buildup of charge and the formation of local electrical dipoles. These can interact with neighboring molecular chains. As a consequence, collections of ''molecular electrical wires'' can show distinctly different characteristics than ''classical electrical wires''. German Science Foundation GRK 1640.

Advances in ultrasensitive mass spectrometry of organic molecules.

Science.gov (United States)

Kandiah, Mathivathani; Urban, Pawel L

2013-06-21

Ultrasensitive mass spectrometric analysis of organic molecules is important for various branches of chemistry, and other fields including physics, earth and environmental sciences, archaeology, biomedicine, and materials science. It finds applications--as an enabling tool--in systems biology, biological imaging, clinical analysis, and forensics. Although there are a number of technical obstacles associated with the analysis of samples by mass spectrometry at ultratrace level (for example analyte losses during sample preparation, insufficient sensitivity, ion suppression), several noteworthy developments have been made over the years. They include: sensitive ion sources, loss-free interfaces, ion optics components, efficient mass analyzers and detectors, as well as "smart" sample preparation strategies. Some of the mass spectrometric methods published to date can achieve sensitivity which is by several orders of magnitude higher than that of alternative approaches. Femto- and attomole level limits of detection are nowadays common, while zepto- and yoctomole level limits of detection have also been reported. We envision that the ultrasensitive mass spectrometric assays will soon contribute to new discoveries in bioscience and other areas.

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

Science.gov (United States)

Millan, M.; Szopa, C.; Buch, A.; Belmahdi, I.; Glavin, D. P.; Freissinet, C.; Eigenbrode, J. L.; Archer, P. D., Jr,; Sutter, B.; Mahaffy, P.

2017-01-01

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Some remarks on non-planar Feynman diagrams

International Nuclear Information System (INIS)

Bielas, Krzysztof; Dubovyk, Ievgen; Gluza, Janusz

2013-12-01

Two criteria for planarity of a Feynman diagram upon its propagators (momentum ows) are presented. Instructive Mathematica programs that solve the problem and examples are provided. A simple geometric argument is used to show that while one can planarize non-planar graphs by embedding them on higher-genus surfaces (in the example it is a torus), there is still a problem with defining appropriate dual variables since the corresponding faces of the graph are absorbed by torus generators.

Some remarks on non-planar Feynman diagrams

Energy Technology Data Exchange (ETDEWEB)

Bielas, Krzysztof; Dubovyk, Ievgen; Gluza, Janusz [Silesia Univ., Katowice (Poland). Inst. of Physics; Riemann, Tord [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany)

2013-12-15

Two criteria for planarity of a Feynman diagram upon its propagators (momentum ows) are presented. Instructive Mathematica programs that solve the problem and examples are provided. A simple geometric argument is used to show that while one can planarize non-planar graphs by embedding them on higher-genus surfaces (in the example it is a torus), there is still a problem with defining appropriate dual variables since the corresponding faces of the graph are absorbed by torus generators.

Single Molecule Study of DNA Organization and Recombination

Science.gov (United States)

Xiao, Botao

We have studied five projects related to DNA organization and recombination using mainly single molecule force-spectroscopy and statistical tools. First, HU is one of the most abundant DNA-organizing proteins in bacterial chromosomes and participates in gene regulation. We report experiments that study the dependence of DNA condensation by HU on force, salt and HU concentration. A first important result is that at physiological salt levels, HU only bends DNA, resolving a previous paradox of why a chromosome-compacting protein should have a DNA-stiffening function. A second major result is quantitative demonstration of strong dependencies of HU-DNA dissociation on both salt concentration and force. Second, we have used a thermodynamic Maxwell relation to count proteins driven off large DNAs by tension, an effect important to understanding DNA organization. Our results compare well with estimates of numbers of proteins HU and Fis in previous studies. We have also shown that a semi-flexible polymer model describes our HU experimental data well. The force-dependent binding suggests mechano-chemical mechanisms for gene regulation. Third, the elusive role of protein H1 in chromatin has been clarified with purified H1 and Xenopus extracts. We find that H1 compacts DNA by both bending and looping. Addition of H1 enhances chromatin formation and maintains the plasticity of the chromatin. Fourth, the topology and mechanics of DNA twisting are critical to DNA organization and recombination. We have systematically measured DNA extension as a function of linking number density from 0.08 to -2 with holding forces from 0.2 to 2.4 pN. Unlike previous proposals, the DNA extension decreases with negative linking number. Finally, DNA recombination is a dynamic process starting from enzyme-DNA binding. We report that the Int-DBD domain of lambda integrase binds to DNA without compaction at low Int-DBD concentration. High concentration of Int-DBD loops DNA below a threshold force

Band-selective excited ultrahigh resolution PSYCHE-TOCSY: fast screening of organic molecules and complex mixtures.

Science.gov (United States)

Kakita, Veera Mohana Rao; Vemulapalli, Sahithya Phani Babu; Bharatam, Jagadeesh

2016-04-01

Precise assignments of (1) H atomic sites and establishment of their through-bond COSY or TOCSY connectivity are crucial for molecular structural characterization by using (1) H NMR spectroscopy. However, this exercise is often hampered by signal overlap, primarily because of (1) H-(1) H scalar coupling multiplets, even at typical high magnetic fields. The recent developments in homodecoupling strategies for effectively suppressing the coupling multiplets into nice singlets (pure-shift), particularly, Morris's advanced broadband pure-shift yielded by chirp excitation (PSYCHE) decoupling and ultrahigh resolution PSYCHE-TOCSY schemes, have shown new possibilities for unambiguous structural elucidation of complex organic molecules. The superior broadband PSYCHE-TOCSY exhibits enhanced performance over the earlier TOCSY methods, which however warrants prolonged experimental times due to the requirement of large number of dwell increments along the indirect dimension. Herein, we present fast and band-selective analog of the broadband PSYCHE-TOCSY, which is useful for analyzing complex organic molecules that exhibit characteristic yet crowded spectral regions. The simple pulse scheme relies on band-selective excitation (BSE) followed by PSYCHE homodecoupling in the indirect dimension. The BSE-PSYCHE-TOCSY has been exemplified for Estradiol and a complex carbohydrate mixture comprised of six constituents of closely comparable molecular weights. The experimental times are greatly reduced viz., ~20 fold for Estradiol and ~10 fold for carbohydrate mixture, with respect to the broadband PSYCHE-TOCSY. Furthermore, unlike the earlier homonuclear band-selective decoupling, the BSE-PSYCHE-decoupling provides fully decoupled pure-shift spectra for all the individual chemical sites within the excited band. The BSE-PSYCHE-TOCSY is expected to have significant potential for quick screening of complex organic molecules and mixtures at ultrahigh resolution. Copyright © 2015 John Wiley

Planarity certification of ATLAS Micromegas detector panels

Energy Technology Data Exchange (ETDEWEB)

Mueller, Ralph; Biebel, Otmar; Bortfeldt, Jonathan; Flierl, Bernhard; Hertenberger, Ralf; Loesel, Philipp; Herrmann, Maximilian [LMU Muenchen (Germany); Zibell, Andre [JMU Wuerzburg (Germany)

2016-07-01

During the second long LHC shutdown, 2019/20, the precision tracking detectors of the ATLAS muon spectrometer in the inner end caps will be replaced using Micromegas, a planar gas-detector technology. Modules of 2 m{sup 2} area are built in quadruplets from five precisely planar sandwich panels that define the anodes and the cathodes of the four active detector planes. A panel is composed of three consecutive layers FR4 - aluminum honeycomb - FR4. Single plane spatial particle resolution below 100 μm is achievable when the deviations from planarity of the strip-anodes do not exceed 80 μm RMS over the whole active area and the parallelism of the readout strips is within 30 μm. In order to measure the dimensional accuracy of each panel, laser distance sensors combined with a coordinate measurement system have been investigated. The sensor requirements to measure the planarity of the panels are a resolution of 0.3 μm and a beam spot diameter of ∼20 μm, well below 100 μ m the size of the smallest structures. We report on achieved planarities of the panels and the performance of the laser sensor system. A panel with an RMS better than 30 μm was build and the evolution of its planarity due to humidity and temperature effects is shown.

Use of a commercially available nucleating agent to control the morphological development of solution-processed small molecule bulk heterojunction organic solar cells

KAUST Repository

Sharenko, Alexander; Treat, Neil D.; Love, John A.; Toney, Michael F.; Stingelin, Natalie; Nguyen, Thuc-Quyen

2014-01-01

© the Partner Organisations 2014. The nucleating agent DMDBS is used to modulate the crystallization of solution-processed small molecule donor molecules in bulk heterojunction organic photovoltaic (BHJ OPV) devices. This control over donor molecule crystallization leads to a reduction in optimized thermal annealing times as well as smaller donor molecule crystallites, and therefore more efficient devices, when using an excessive amount of solvent additive. We therefore demonstrate the use of nucleating agents as a powerful and versatile processing strategy for solution-processed, small molecule BHJ OPVs. This journal is

Use of a commercially available nucleating agent to control the morphological development of solution-processed small molecule bulk heterojunction organic solar cells

KAUST Repository

Sharenko, Alexander

2014-08-12

© the Partner Organisations 2014. The nucleating agent DMDBS is used to modulate the crystallization of solution-processed small molecule donor molecules in bulk heterojunction organic photovoltaic (BHJ OPV) devices. This control over donor molecule crystallization leads to a reduction in optimized thermal annealing times as well as smaller donor molecule crystallites, and therefore more efficient devices, when using an excessive amount of solvent additive. We therefore demonstrate the use of nucleating agents as a powerful and versatile processing strategy for solution-processed, small molecule BHJ OPVs. This journal is

Yangian-type symmetries of non-planar leading singularities

Energy Technology Data Exchange (ETDEWEB)

Frassek, Rouven [Department of Mathematical Sciences, Durham University,South Road, Durham DH1 3LE (United Kingdom); Meidinger, David [Institut für Mathematik und Institut für Physik, Humboldt-Universität zu Berlin,Zum Großen Windkanal 6, 12489 Berlin (Germany)

2016-05-18

We take up the study of integrable structures behind non-planar contributions to scattering amplitudes in N = 4 super Yang-Mills theory. Focusing on leading singularities, we derive the action of the Yangian generators on color-ordered subsets of the external states. Each subset corresponds to a single boundary of the non-planar on-shell diagram. While Yangian invariance is broken, we find that higher-level Yangian generators still annihilate the non-planar on-shell diagram. For a given diagram, the number of these generators is governed by the degree of non-planarity. Furthermore, we present additional identities involving integrable transfer matrices. In particular, for diagrams on a cylinder we obtain a conservation rule similar to the Yangian invariance condition of planar on-shell diagrams. To exemplify our results, we consider a five-point MHV on-shell function on a cylinder.

Leucine-rich repeat-containing synaptic adhesion molecules as organizers of synaptic specificity and diversity.

Science.gov (United States)

Schroeder, Anna; de Wit, Joris

2018-04-09

The brain harbors billions of neurons that form distinct neural circuits with exquisite specificity. Specific patterns of connectivity between distinct neuronal cell types permit the transfer and computation of information. The molecular correlates that give rise to synaptic specificity are incompletely understood. Recent studies indicate that cell-surface molecules are important determinants of cell type identity and suggest that these are essential players in the specification of synaptic connectivity. Leucine-rich repeat (LRR)-containing adhesion molecules in particular have emerged as key organizers of excitatory and inhibitory synapses. Here, we discuss emerging evidence that LRR proteins regulate the assembly of specific connectivity patterns across neural circuits, and contribute to the diverse structural and functional properties of synapses, two key features that are critical for the proper formation and function of neural circuits.

Biological response of HeLa cells to gold nanoparticles coated with organic molecules.

Science.gov (United States)

Cardoso Avila, P E; Rangel Mendoza, A; Pichardo Molina, J L; Flores Villavicencio, L L; Castruita Dominguez, J P; Chilakapati, M K; Sabanero Lopez, M

2017-08-01

In this work, gold nanospheres functionalized with low weight organic molecules (4-aminothiphenol and cysteamine) were synthesized in a one-step method for their in vitro cytotoxic evaluation on HeLa cells. To enhance the biocompatibility of the cysteamine-capped GNPs, BSA was used due to its broad PH stability and high binding affinity to gold nanoparticles. Besides, the widely reported silica coated gold nanorods were tested here to contrast their toxic response against our nanoparticles coated with organic molecules. Our results shown, the viability measured at 1.9×10 -5 M did not show significant differences against negative controls for all the samples; however, the metabolic activity of HeLa cells dropped when they were exposed to silica gold nanorods in the range of concentrations from 2.9×10 -7 M to 3.0×10 -4 M, while in the cases of gold nanospheres, we found that only at concentrations below 1.9×10 -5 M metabolic activity was normal. Our preliminary results did not indicate any perceivable harmful toxicity to cell membrane, cytoskeleton or nucleus due to our nanospheres at 1.9×10 -5 M. Additional test should be conducted in order to ensure a safe use of them for biological applications, and to determine the extent of possible damage. Copyright © 2017 Elsevier Ltd. All rights reserved.

Exploring molecular complexity with ALMA (EMoCA): Deuterated complex organic molecules in Sagittarius B2(N2)

Science.gov (United States)

Belloche, A.; Müller, H. S. P.; Garrod, R. T.; Menten, K. M.

2016-03-01

Context. Deuteration is a powerful tracer of the history of the cold prestellar phase in star-forming regions. Apart from methanol, little is known about deuterium fractionation of complex organic molecules in the interstellar medium, especially in regions forming high-mass stars. Aims: Our goal is to detect deuterated complex organic molecules toward the high mass star-forming region Sagittarius B2 (Sgr B2) and derive the level of deuteration for these molecules. Methods: We use a complete 3-mm spectral line survey performed with the Atacama Large Millimeter/submillimeter Array (ALMA) to search for deuterated complex organic molecules toward the hot molecular core Sgr B2(N2). We constructed population diagrams and integrated intensity maps to fit rotational temperatures and emission sizes for each molecule. Column densities are derived by modeling the full spectrum under the assumption of local thermodynamic equilibrium. We compare the results to predictions of two astrochemical models that treat the deuteration process. Results: We report the detection of CH2DCN toward Sgr B2(N2) with a deuteration level of 0.4%, and tentative detections of CH2DOH, CH2DCH2CN, the chiral molecule CH3CHDCN, and DC3N with levels in the range 0.05%-0.12%. A stringent deuteration upper limit is obtained for CH3OD (cyanide, the four deuterated species of ethanol, and CH2DOCHO. Ethyl cyanide is less deuterated than methyl cyanide by at least a factor five. The [CH2DOH]/[CH3OD] abundance ratio is higher than 1.8. It may still be consistent with the value obtained in Orion KL. Except for methyl cyanide, the measured deuteration levels lie at least a factor four below the predictions of current astrochemical models. The deuteration levels in Sgr B2(N2) are also lower than in Orion KL by a factor of a few up to a factor ten. Conclusions: The discrepancy between the deuteration levels of Sgr B2(N2) and the predictions of chemical models, and the difference between Sgr B2(N2) and Orion KL may

ytterbium- & erbium-doped silica for planar waveguide lasers & amplifiers

DEFF Research Database (Denmark)

Dyndgaard, Morten Glarborg

2001-01-01

The purpose of this work was to demonstrate ytterbium doped planar components and investigate the possibilities of making erbium/ytterbium codoped planar waveguides in germano-silica glass. Furthermore, tools for modelling lasers and erbium/ytterbium doped amplifiers. The planar waveguides were...

Planar Poincare chart - A planar graphic representation of the state of light polarization

Science.gov (United States)

Tedjojuwono, Ken K.; Hunter, William W., Jr.; Ocheltree, Stewart L.

1989-01-01

The planar Poincare chart, which represents the complete planar equivalence of the Poincare sphere, is proposed. The four sets of basic lines are drawn on two separate charts for the generalization and convenience of reading the scale. The chart indicates the rotation of the principal axes of linear birefringent material. The relationships between parameters of the two charts are given as 2xi-2phi (orientation angle of the major axis-ellipticity angle) pair and 2alpha-delta (angle of amplitude ratio-phase difference angle) pair. The results are useful for designing and analyzing polarization properties of optical components with birefringent properties.

Synthesis of an A-D-A type of molecule used as electron acceptor for improving charge transfer in organic solar cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao-Zhi, E-mail: chzhzhang@sohu.com [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Gu, Shu-Duo; Shen, Dan; Yuan, Yang [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Zhang, Mingdao, E-mail: matchlessjimmy@163.com [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China)

2016-08-22

Electron-accepting molecules play an important role in developing organic solar cells. A new type of A-D-A molecule, 3,6-di([7-(5-bromothiophen-2-yl)-1,5,2,4,6,8-dithiotetrazocin-3-yl]thiophen -2-yl)-9-(2-ethylhexyl)carbazole, was synthesized. The lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels are −3.55 and −5.85 eV, respectively. Therefore, the A-D-A type of compound could be used as electron acceptor for fabricating organic solar cell with a high open circuit voltage. Gibbs free energy (−49.2 kJ/mol) reveals that the process of A-D-A acceptor accepting an electron from poly(3-hexylthiophene) at excited state is spontaneous. The value of entropy (118 J/mol) in the process of an electron transferring from P3HT to the A-D-A acceptor at organic interface suggests that electrons generated from separation of electron-hole pairs at donor/acceptor interface would be delocalized efficiently. Therefore, the A-D-A molecule would be a potential acceptor for efficient organic BHJ solar cells.

Superposed Redox Chemistry of Fused Carbon Rings in Cyclooctatetraene-Based Organic Molecules for High-Voltage and High-Capacity Cathodes.

Science.gov (United States)

Zhao, Xiaolin; Qiu, Wujie; Ma, Chao; Zhao, Yingqin; Wang, Kaixue; Zhang, Wenqing; Kang, Litao; Liu, Jianjun

2018-01-24

Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N-O, C═X (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C 8 H 8 ) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C 8 -C 4 -C 8 (C 16 H 12 ) and C 8 -C 4 -C 8 -C 4 -C 8 (C 24 H 16 ) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C 16 H 12 and C 24 H 16 exhibit discharge capacities of 525.3 and 357.2 mA h g -1 at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na + /Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C 24 H 16 -based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C 4 ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.

The census of complex organic molecules in the solar-type protostar IRAS16293-2422

Energy Technology Data Exchange (ETDEWEB)

Jaber, Ali A.; Ceccarelli, C.; Kahane, C. [Université Grenoble Alpes, IPAG, F-38000 Grenoble (France); Caux, E. [Université de Toulouse, UPS-OMP, IRAP, F-31400 Toulouse (France)

2014-08-10

Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (≳30-40 K) and released in the gas phase at dust temperatures of ≳100 K. However, recent detections of COMs in ≲20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we present a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (≲30 K) envelope of IRAS16293-2422, with abundances of 0.03-2 × 10{sup –10}. Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.

Detection and mapping of organic molecules in Titan's atmosphere using ALMA

Science.gov (United States)

Cordiner, Martin

2016-06-01

Titan's atmospheric photochemistry results in the production of a wide range of organic molecules, including hydrocarbons, nitriles, aromatics and other complex species of possible pre-biotic relevance. Studies of Titan's atmospheric chemistry thus provide a unique opportunity to explore the origin and evolution of organic matter in primitive (terrestrial) planetary atmospheres. The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful new facility, well suited to the study of molecular emission from Titan's upper and middle-atmosphere. Results will be presented from our ongoing studies of Titan using ALMA data obtained during the period 2012-2014 [1,2], including detection and mapping of emission from C2H5CN, HNC, HC3N, CH3CN and CH3CCH. In addition, combining data from multiple ALMA Band 6 observations, we obtained high-resolution spectra with unprecedented sensitivity, enabling the first detection of C2H3CN (vinyl cyanide) on Titan, and derived a mean C2H3CN C2H5CN abundance ratio above 300 km of 0.3. Vinyl cyanide has recently been investigated as a possible constituent of (pre-biotic) vesicle membranes in Titan's liquid CH4 oceans [3]. Radiative transfer models and possible chemical formation pathways for the detected molecules will be discussed. ALMA observations provide instantaneous snapshot mapping of Titan's entire Earth-facing hemisphere for gases inaccessible to previous studies, and therefore provide new insights into photochemical production and transport, particularly at higher altitudes. Our maps show spatially resolved peaks in Titan's northern and southern hemispheres, consistent with the molecular distributions found in previous studies at infrared wavelengths by Voyager and Cassini, but high-altitude longitudinal asymmetries in our nitrile data indicate that the mesosphere may be more spatially variable than previously thought.

Vibronic coupling in ionized organic molecules. Structural distortions and chemical reactions

International Nuclear Information System (INIS)

Williams, F.

2002-01-01

Complete text of publication follows. Ionized organic molecules (radical cations, RC) are prone to undergo vibronic coupling whenever there is a relatively small energy gap ( 2v point group of the neutral parent molecule by twisting at the olefinic π bond to the lower C 2 symmetry in the RC (Chem. Eur. J. 2002, 8, 1074). These experiments clearly revealed a double minimum in the potential energy surface along the a 2 torsional mode. This is in accord with the coupling of the 2 B 1 and 2 B 2 Born-Oppenheimer states in C 2v symmetry, this mixing of the 2 B 1 π-ionized ground state and the 2 B 2 δ-ionized excited state being facilitated by the low (∼ 1.0 eV) gap between these states, as estimated from photoelectron spectroscopy. Turning to the second class of RC where unimolecular rearrangement reactions are promoted by vibronic interaction, several cases have emerged where the rearrangement would not be expected if it were based only on the ground-state properties of the RC. It was found (Chem. Phy. Lett. 1988, 143, 521) that the ethylene oxide RC undergoes C-C ring opening to the oxallyl species despite the fact that the ground state corresponds to ionization from the nonbonding oxygen π lone-pair orbital. The reaction develops excited-state character as a result of the vibronic mixing so that the activation barrier to ring opening is lowered. We will discuss the unusual rearrangements of the bicyclo[1.1.1.]pentane and [1.1.1]propellane RC from a similar perspective, emphasis being placed on the decisive role of symmetry in predicting the course of these rearrangements. We illustrate how this approach can reconcile conflicting considerations on some of the 'unexpected' reaction pathways followed by highly strained organic RC

Complex organic molecules in strongly UV-irradiated gas

Science.gov (United States)

Cuadrado, S.; Goicoechea, J. R.; Cernicharo, J.; Fuente, A.; Pety, J.; Tercero, B.

2017-07-01

We investigate the presence of complex organic molecules (COMs) in strongly UV-irradiated interstellar molecular gas. We have carried out a complete millimetre (mm) line survey using the IRAM 30 m telescope towards the edge of the Orion Bar photodissociation region (PDR), close to the H2 dissociation front, a position irradiated by a very intense far-UV (FUV) radiation field. These observations have been complemented with 8.5'' resolution maps of the H2CO JKa,Kc = 51,5 → 41,4 and C18O J = 3 → 2 emission at 0.9 mm. Despite being a harsh environment, we detect more than 250 lines from COMs and related precursors: H2CO, CH3OH, HCO, H2CCO, CH3CHO, H2CS, HCOOH, CH3CN, CH2NH, HNCO, H213CO, and HC3N (in decreasing order of abundance). For each species, the large number of detected lines allowed us to accurately constrain their rotational temperatures (Trot) and column densities (N). Owing to subthermal excitation and intricate spectroscopy of some COMs (symmetric- and asymmetric-top molecules such as CH3CN and H2CO, respectively), a correct determination of N and Trot requires building rotational population diagrams of their rotational ladders separately. The inferred column densities are in the 1011-1013 cm-2 range. We also provide accurate upper limit abundances for chemically related molecules that might have been expected, but are not conclusively detected at the edge of the PDR (HDCO, CH3O, CH3NC, CH3CCH, CH3OCH3, HCOOCH3, CH3CH2OH, CH3CH2CN, and CH2CHCN). A non-thermodynamic equilibrium excitation analysis for molecules with known collisional rate coefficients suggests that some COMs arise from different PDR layers but we cannot resolve them spatially. In particular, H2CO and CH3CN survive in the extended gas directly exposed to the strong FUV flux (Tk = 150-250 K and Td≳ 60 K), whereas CH3OH only arises from denser and cooler gas clumps in the more shielded PDR interior (Tk = 40-50 K). The non-detection of HDCO towards the PDR edge is consistent with the

Intracellular Delivery of a Planar DNA Origami Structure by the Transferrin-Receptor Internalization Pathway.

Science.gov (United States)

Schaffert, David H; Okholm, Anders H; Sørensen, Rasmus S; Nielsen, Jesper S; Tørring, Thomas; Rosen, Christian B; Kodal, Anne Louise B; Mortensen, Michael R; Gothelf, Kurt V; Kjems, Jørgen

2016-05-01

DNA origami provides rapid access to easily functionalized, nanometer-sized structures making it an intriguing platform for the development of defined drug delivery and sensor systems. Low cellular uptake of DNA nanostructures is a major obstacle in the development of DNA-based delivery platforms. Herein, significant strong increase in cellular uptake in an established cancer cell line by modifying a planar DNA origami structure with the iron transport protein transferrin (Tf) is demonstrated. A variable number of Tf molecules are coupled to the origami structure using a DNA-directed, site-selective labeling technique to retain ligand functionality. A combination of confocal fluorescence microscopy and quantitative (qPCR) techniques shows up to 22-fold increased cytoplasmic uptake compared to unmodified structures and with an efficiency that correlates to the number of transferrin molecules on the origami surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic molecules as tools to control the growth, surface structure, and redox activity of colloidal quantum dots.

Science.gov (United States)

Weiss, Emily A

2013-11-19

In order to achieve efficient and reliable technology that can harness solar energy, the behavior of electrons and energy at interfaces between different types or phases of materials must be understood. Conversion of light to chemical or electrical potential in condensed phase systems requires gradients in free energy that allow the movement of energy or charge carriers and facilitate redox reactions and dissociation of photoexcited states (excitons) into free charge carriers. Such free energy gradients are present at interfaces between solid and liquid phases or between inorganic and organic materials. Nanostructured materials have a higher density of these interfaces than bulk materials. Nanostructured materials, however, have a structural and chemical complexity that does not exist in bulk materials, which presents a difficult challenge: to lower or eliminate energy barriers to electron and energy flux that inevitably result from forcing different materials to meet in a spatial region of atomic dimensions. Chemical functionalization of nanostructured materials is perhaps the most versatile and powerful strategy for controlling the potential energy landscape of their interfaces and for minimizing losses in energy conversion efficiency due to interfacial structural and electronic defects. Colloidal quantum dots are semiconductor nanocrystals synthesized with wet-chemical methods and coated in organic molecules. Chemists can use these model systems to study the effects of chemical functionalization of nanoscale organic/inorganic interfaces on the optical and electronic properties of a nanostructured material, and the behavior of electrons and energy at interfaces. The optical and electronic properties of colloidal quantum dots have an intense sensitivity to their surface chemistry, and their organic adlayers make them dispersible in solvent. This allows researchers to use high signal-to-noise solution-phase spectroscopy to study processes at interfaces. In this

Layered Zinc Hydroxide Salts Intercalated with Anionic Surfactants and Adsolubilized with UV Absorbing Organic Molecules

OpenAIRE

Cursino,Ana C. T.; Rives,Vicente; Carlos,Luís D.; Rocha,João; Wypych,Fernando

2015-01-01

Two anionic surfactants, dodecylsulfate (DDS) and dodecylbenzenesulfonate (DBS), were intercalated into layered zinc hydroxide salts (LHS) using the direct alkaline co-precipitation method, and characterized by powder X-ray diffraction (PXRD), Fourier-transform infrared (FTIR) and thermogravimetric analysis/differential thermal analysis (TGA/DTA). Different UV-absorbing organic molecules, like salicylates, cinnamates and benzophenones, were adsolubilized in the LHS interlayer following two di...

The wetting of planar solid surfaces by symmetric binary mixtures near bulk gas-liquid coexistence

International Nuclear Information System (INIS)

Woywod, Dirk; Schoen, Martin

2004-01-01

We investigate the wetting of planar, nonselective solid substrates by symmetric binary mixtures where the attraction strength between like molecules of components A and B is the same, that is ε AA ε BB AB vertical bar ≤ vertical bar ε AA vertical bar, that is by varying the attraction between a pair of unlike molecules. By means of mean-field lattice density functional calculations we observe a rich wetting behaviour as a result of the interplay between ε AB and the attraction of fluid molecules by the solid substrate ε W . In accord with previous studies we observe complete wetting only above the critical end point if the bulk mixture exhibits a moderate to weak tendency to liquid-liquid phase separation even for relatively strong fluid-substrate attraction. However, in this case layering transitions may arise below the temperature of the critical end point. For strongly phase separating mixtures complete wetting is observed for all temperatures T ≥0 along the line of discontinuous phase transitions in the bulk

Flat panel planar optic display

Energy Technology Data Exchange (ETDEWEB)

Veligdan, J.T. [Brookhaven National Lab., Upton, NY (United States). Dept. of Advanced Technology

1994-11-01

A prototype 10 inch flat panel Planar Optic Display, (POD), screen has been constructed and tested. This display screen is comprised of hundreds of planar optic class sheets bonded together with a cladding layer between each sheet where each glass sheet represents a vertical line of resolution. The display is 9 inches wide by 5 inches high and approximately 1 inch thick. A 3 milliwatt HeNe laser is used as the illumination source and a vector scanning technique is employed.

Interface Engineering of Organic Schottky Barrier Solar Cells and Its Application in Enhancing Performances of Planar Heterojunction Solar Cells

Science.gov (United States)

Jin, Fangming; Su, Zisheng; Chu, Bei; Cheng, Pengfei; Wang, Junbo; Zhao, Haifeng; Gao, Yuan; Yan, Xingwu; Li, Wenlian

2016-05-01

In this work, we describe the performance of organic Schottky barrier solar cells with the structure of ITO/molybdenum oxide (MoOx)/boron subphthalocyanine chloride (SubPc)/bathophenanthroline (BPhen)/Al. The SubPc-based Schottky barrier solar cells exhibited a short-circuit current density (Jsc) of 2.59 mA/cm2, an open-circuit voltage (Voc) of 1.06 V, and a power conversion efficiency (PCE) of 0.82% under simulated AM1.5 G solar illumination at 100 mW/cm2. Device performance was substantially enhanced by simply inserting thin organic hole transport material into the interface of MoOx and SubPc. The optimized devices realized a 180% increase in PCE of 2.30% and a peak Voc as high as 1.45 V was observed. We found that the improvement is due to the exciton and electron blocking effect of the interlayer and its thickness plays a vital role in balancing charge separation and suppressing quenching effect. Moreover, applying such interface engineering into MoOx/SubPc/C60 based planar heterojunction cells substantially enhanced the PCE of the device by 44%, from 3.48% to 5.03%. Finally, we also investigated the requirements of the interface material for Schottky barrier modification.

Inkjet-Printed Small-Molecule Organic Light-Emitting Diodes: Halogen-Free Inks, Printing Optimization, and Large-Area Patterning.

Science.gov (United States)

Zhou, Lu; Yang, Lei; Yu, Mengjie; Jiang, Yi; Liu, Cheng-Fang; Lai, Wen-Yong; Huang, Wei

2017-11-22

Manufacturing small-molecule organic light-emitting diodes (OLEDs) via inkjet printing is rather attractive for realizing high-efficiency and long-life-span devices, yet it is challenging. In this paper, we present our efforts on systematical investigation and optimization of the ink properties and the printing process to enable facile inkjet printing of conjugated light-emitting small molecules. Various factors on influencing the inkjet-printed film quality during the droplet generation, the ink spreading on the substrates, and its solidification processes have been systematically investigated and optimized. Consequently, halogen-free inks have been developed and large-area patterning inkjet printing on flexible substrates with efficient blue emission has been successfully demonstrated. Moreover, OLEDs manufactured by inkjet printing the light-emitting small molecules manifested superior performance as compared with their corresponding spin-cast counterparts.

Single-molecule conductivity of non-redox and redox molecules at pure and gold-mined Au(111)-electrode surfaces

DEFF Research Database (Denmark)

Zhang, Jingdong; Chi, Qijin; Ulstrup, Jens

The structure, two-dimensional organization, and function of molecules immobilized on solid surfaces can be addressed in a degree of detail that has reached the level of the single-molecule. In this context redox molecules are “smart” molecules adding sophisticated electronic function. Redox meta...

Synthesis of Conjugated Small Molecules and Polymers by a Palladium Catalyzed Cyclopentannulation Strategy: Towards New Organic Semiconductors

Science.gov (United States)

Bheemireddy, Sambasiva Reddy

The utility of conjugated small molecules and polymers as organic semiconductors have seen a tremendous growth in research and development in academia as well as industry because of their processability and flexibility advantages in comparison to inorganic semiconductors. The extensive research over the years has produced a large number of p-type (hole conducting) and n-type (electron conducting) semiconductors that can be used to construct organic electronic devices. Of these materials, p-type semiconductors are more established and extensively studied because of the ease of preparation as well as their better general stability in comparison to n-type materials. Despite recent research into the development of n-type materials, fullerene (C60 and C 70) and its derivatives are still the predominant materials used as electron acceptors for OPV applications. By taking advantage of the electron accepting behavior of cyclopenta[hi]aceanthrylene fragment of C70, we have designed and synthesized new materials based on cyclopenta-fused polycyclic aromatic hydrocarbons (CP-PAHs). By using a newly developed palladium catalyzed cyclopentannulation methodology, 1,2,6,7- tetraarylcyclopenta[hi]aceanthrylenes were prepared by treating diarylethynylenes with 9,10-dibromoanthracene. Scholl cyclodehydrogenation was used to close the externally fused aryl groups to provide access to contorted 2,7,13,18- tetraalkoxytetrabenzo[f,h,r,t]rubicenes. The contortion provides access to more soluble materials than their planar counterparts but still ii allows significant pi-pi stacking between molecules. Using a modified palladium catalyzed cyclopentannulation polymerization followed by a cyclodehydrogenation reaction, a nonconventional synthesis of CP-PAH embedded ladder polymers was also achieved. These ladder polymers possess broad UV-Vis absorptions and narrow optical gaps of 1.17-1.29 eV. The synthesis of new donor-acceptor copolymers incorporating electron accepting 1,2,6,7- tetra(4

Planar Algebra of the Subgroup-Subfactor

Indian Academy of Sciences (India)

The crucial step in this identification is an exhibition of a model for the basic construction tower, and thereafter of the standard invariant of R ⋊ H ⊂ R ⋊ G in terms of operator matrices. We also obtain an identification between the planar algebra of the fixed algebra subfactor R G ⊂ R H and the -invariant planar subalgebra ...

Technical errors in planar bone scanning.

Science.gov (United States)

Naddaf, Sleiman Y; Collier, B David; Elgazzar, Abdelhamid H; Khalil, Magdy M

2004-09-01

Optimal technique for planar bone scanning improves image quality, which in turn improves diagnostic efficacy. Because planar bone scanning is one of the most frequently performed nuclear medicine examinations, maintaining high standards for this examination is a daily concern for most nuclear medicine departments. Although some problems such as patient motion are frequently encountered, the degraded images produced by many other deviations from optimal technique are rarely seen in clinical practice and therefore may be difficult to recognize. The objectives of this article are to list optimal techniques for 3-phase and whole-body bone scanning, to describe and illustrate a selection of deviations from these optimal techniques for planar bone scanning, and to explain how to minimize or avoid such technical errors.

Improved detection limits of bacterial endotoxins using new type of planar interdigital sensors

KAUST Repository

Syaifudin, A. R Mohd

2012-10-01

New types of planar interdigital sensors were fabricated by photolithography and etching techniques on a Silicon/Silicon Dioxide (Si/SiO2) wafer (single side polished). The sensors were then coated with APTES (3-aminopropyltrietoxysilane) a cross linker used to bind Polymyxin B (PmB) molecules on electrodes surface. PmB is an antimicrobial peptide produced by the Gram-positive bacterium-Bacillus which has specific binding properties to Lipopolysaccharide (LPS). This paper will discuss the fabrication process, coating and immobilization procedures and analysis of sensors\\' performance based on Impedance Spectroscopy method. The sensor sensitivity was compared to standard ToxinSensor Chromogenic LAL Endotoxin Assay Kit for verification. © 2012 IEEE.

A Planar, Chip-Based, Dual-Beam Refractometer Using an Integrated Organic Light Emitting Diode (OLED) Light Source and Organic Photovoltaic (OPV) Detectors

Science.gov (United States)

Ratcliff, Erin L.; Veneman, P. Alex; Simmonds, Adam; Zacher, Brian; Huebner, Daniel

2010-01-01

We present a simple chip-based refractometer with a central organic light emitting diode (OLED) light source and two opposed organic photovoltaic (OPV) detectors on an internal reflection element (IRE) substrate, creating a true dual-beam sensor platform. For first-generation platforms, we demonstrate the use of a single heterojunction OLED based on electroluminescence emission from an Alq3/TPD heterojunction (tris-(8-hydroxyquinoline)aluminum/N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine) and light detection with planar heterojunction pentacene/C60 OPVs. The sensor utilizes the considerable fraction of emitted light from conventional thin film OLEDs that is coupled into guided modes in the IRE instead of into the forward (display) direction. A ray-optics description is used to describe light throughput and efficiency-limiting factors for light coupling from the OLED into the substrate modes, light traversing through the IRE substrate, and light coupling into the OPV detectors. The arrangement of the OLED at the center of the chip provides for two sensing regions, a “sample” and “reference” channel, with detection of light by independent OPV detectors. This configuration allows for normalization of the sensor response against fluctuations in OLED light output, stability, and local fluctuations (temperature) which might influence sensor response. The dual beam configuration permits significantly enhanced sensitivity to refractive index changes relative to single-beam protocols, and is easily integrated into a field-portable instrumentation package. Changes in refractive index (ΔR.I.) between 10−2 and 10−3 R.I. units could be detected for single channel operation, with sensitivity increased to ΔR.I. ≈ 10−4 units when the dual beam configuration is employed. PMID:20218580

Measurement of the conductance properties of single organic molecules using gold nanoparticles

Science.gov (United States)

Gordin, Yoav

In this work we describe the development and application of a new method for the electrical conductance measurement of single molecules. The issue of reliable theoretical modeling of molecular electronic transport is still very much in debate. The experimental methods used in the field are difficult to realize and interpret; most have very low yield, preventing proper statistical analysis and many have problems in the researchers' ability to characterize the system properly. We address this issue by using self assembly of gold nanoparticle-molecule-gold nanoparticle objects called dimers. This method allows fabrication of molecular junctions with greater ease; moreover it allows individual characterization of the various elements of the junction, removing much of the uncertainties that exist in this kind of measurements. We make use of home grown gold nanoparticles with a few tens of nanometer diameter to form the hybrid dimers. The dimers are large enough to connect between electrodes fabricated using electron beam lithography and to measure the electric properties of the molecule. We have invested significant effort in the characterization of the system, ensuring that the dimers are indeed bridged by the molecules, and that the chances that more than a single molecule exists in a dimer are negligibly small. We have made measurements on single gold nanoparticles, to characterize their properties separately from those of the molecule. These measurements have allowed us to observe single electron transistor (SET) behavior, resulting from the requirement that electrons charge the nanoparticle during transport. We have shown that the energy associated with this charging scales with nanoparticle size as expected. We have performed measurements on single organic molecules, showing that there is a very strong influence of molecular conjugation (the way electronic orbitals are spread along the molecular backbone) on its conductance. The molecules with broken conjugation

Signatures of dynamics in charge transport through organic molecules; Dynamisches Verhalten beim Ladungstransport durch organische Molekuele

Energy Technology Data Exchange (ETDEWEB)

Secker, Daniel

2008-06-03

The aim of the thesis at hand was to investigate dynamical behaviour in charge transport through organic molecules experimentally with the help of the mechanically controlled break junction (MCBJ) technique. the thesis concentrates on the complex interaction between the molecular contact configuration and the electronic structure. it is shown that by variation of the electrode distance and so by a manipulation of the molecule and contact configuration the electronic structure as well as the coupling between the molecule and the electrodes is affected. The latter statement is an additional hint how closely I-V-characteristics depend on the molecular contact configuration. Depending on the applied voltage and so the electric field there are two different configurations preferred by the molecular contact. A potential barrier between these two states is the origin of the hysteresis. A central part of the thesis is dealing with measurements of the current noise. Finally it can be concluded that the detailed discussion reveals the strong effect of dynamical interactions between the atomic configuration of the molecular contact and the electronic structure on the charge transport in single molecule junctions. (orig.)

Multivariate Metal-Organic Frameworks for Dialing-in the Binding and Programming the Release of Drug Molecules.

Science.gov (United States)

Dong, Zhiyue; Sun, Yangzesheng; Chu, Jun; Zhang, Xianzheng; Deng, Hexiang

2017-10-11

We report the control of guest release profiles by dialing-in desirable interactions between guest molecules and pores in metal-organic frameworks (MOFs). The interactions can be derived by the rate constants that were quantitatively correlated with the type of functional group and its proportion in the porous structure; thus the release of guest molecules can be predicted and programmed. Specifically, three probe molecules (ibuprofen, rhodamine B, and doxorubicin) were studied in a series of robust and mesoporous MOFs with multiple functional groups [MIL-101(Fe)-(NH 2 ) x , MIL-101(Fe)-(C 4 H 4 ) x , and MIL-101(Fe)-(C 4 H 4 ) x (NH 2 ) 1-x ]. The release rate can be adjusted by 32-fold [rhodamine from MIL-101(Fe)-(NH 2 ) x ], and the time of release peak can be shifted by up to 12 days over a 40-day release period [doxorubicin from MIL-101(Fe)-(C 4 H 4 ) x (NH 2 ) 1-x ], which was not obtained in the physical mixture of the single component MOF counterparts nor in other porous materials. The corelease of two pro-drug molecules (ibuprofen and doxorubicin) was also achieved.

Developing powerful tritide technique: Organic and biological molecule labeling

International Nuclear Information System (INIS)

Anon.

1991-01-01

Complex hydrides are very important reagents in organic synthesis due to the range of reducing powers and selectivities available from different agents. Unfortunately, the availability of these compounds for radiosynthesis has been extremely limited due to the difficulty of making them with adequate levels of tritium. Investigators at the Lawrence Berkeley Laboratory (LBL) National Tritium Labeling Facility have developed a new addition to the repertoire of the tritium-labeling chemist. The new method allows site-specific incorporation of tritium into organic and biological molecules by efficient reduction processes. Exceptionally reactive and selective reducing agents are prepared and used for labeling in a on-pot process. Three new tritide reagents - supertritide (lithium triethyl borotritide), LiAlT 4 (lithium aluminum tritide), and L-Selectride (sterically hindered lithium tri-sec-butyl borotritide) - have been synthesized at carrier-free levels, and have been demonstrated to be fully reactive. The availability of these versatile and reactive reagents gives the tritium radiochemist great control over chemoselectivity and stereoselectivity. The LBL tritide reagents can drive numerous conventional chemical reactions, and have been used to reduce p-toluene sulfonates, amides, lactones, esters, and aldehydes. These reactions produce good yields and result in products with maximum specific activities. The reagents clearly exhibit superior reactivity and may be used in many more synthetic processes than sodium borohydride, which is the currently used reagent. In addition, tritide reagents such as L-selectride have been shown to give greater control over stereochemistry and selectivity than sodium borohydride

On Longest Cycles in Essentially 4-Connected Planar Graphs

Directory of Open Access Journals (Sweden)

Fabrici Igor

2016-08-01

Full Text Available A planar 3-connected graph G is essentially 4-connected if, for any 3-separator S of G, one component of the graph obtained from G by removing S is a single vertex. Jackson and Wormald proved that an essentially 4-connected planar graph on n vertices contains a cycle C such that . For a cubic essentially 4-connected planar graph G, Grünbaum with Malkevitch, and Zhang showed that G has a cycle on at least ¾ n vertices. In the present paper the result of Jackson and Wormald is improved. Moreover, new lower bounds on the length of a longest cycle of G are presented if G is an essentially 4-connected planar graph of maximum degree 4 or G is an essentially 4-connected maximal planar graph.

Organic Zeolite Analogues Based on Multi-Component Liquid Crystals: Recognition and Transformation of Molecules within Constrained Environments

Directory of Open Access Journals (Sweden)

Yasuhiro Ishida

2011-01-01

Full Text Available In liquid crystals (LCs, molecules are confined in peculiar environments, where ordered alignment and certain mobility are realized at the same time. Considering these characteristics, the idea of “controlling molecular events within LC media” seems reasonable. As a suitable system for investigating this challenge, we have recently developed a new class of ionic LCs; the salts of amphiphilic carboxylic acids with 2-amino alcohols, or those of carboxylic acids with amphiphilic 2-amino alcohols, have a strong tendency to exhibit thermotropic LC phases. Because of the noncovalent nature of the interaction between molecules, one of the two components can easily be exchanged with, or transformed into, another molecule, without distorting the original LC architecture. In addition, both components are common organic molecules, and a variety of compounds are easily available. Taking advantage of these characteristics, we have succeeded in applying two‑component LCs as chiral media for molecular recognition and reactions. This review presents an overview of our recent studies, together with notable reports related to this field.

Probing the emitter site of Renilla luciferase using small organic molecules; an attempt to understand the molecular architecture of the emitter site.

Science.gov (United States)

Salehi, Farajollah; Emamzadeh, Rahman; Nazari, Mahboobeh; Rasa, Seyed Mohammad Mahdi

2016-12-01

Renilla luciferase is a sensitive enzyme and has wide applications in biotechnology such as drug screening. Previous studies have tried to show the catalytic residues, nevertheless, the accurate architecture and molecular behavior of its emitter site remains uncharacterized. In this study, the activity of Renilla luciferase, in the presence of two small organic molecules including dimethyl sulfoxide (DMSO) and isopropanol was considered and the structure was studied by circular dichroism (CD) and fluorescence spectroscopy. Moreover, the interaction of small organic molecules with the Renilla luciferase was studied using molecular dynamics simulations. Kinetics studies showed that at low concentration of DMSO (16.6-66mM) and isopropanol (19.3-76mM) the K m changed and a competitive inhibition pattern was observed. Moreover, spectroscopy studies reveled that the changes of activity of Renilla luciferase in the presence of low concentrations of small organic molecules was not associated with structural collapse or severe changes in the enzyme conformation. Molecular dynamics simulations indicated that DMSO and isopropanol, as probing molecules, were both able to bind to the emitter site and remained with the residues of the emitter site. Based on the probing data, the architecture of the emitter site in the "non-binding" model was proposed. Copyright © 2016 Elsevier B.V. All rights reserved.

Planar half-cell shaped precursor body

DEFF Research Database (Denmark)

2015-01-01

The invention relates to a half-cell shaped precursor body of either anode type or cathode type, the half-cell shaped precursor body being prepared to be free sintered to form a sintered or pre-sintered half-cell being adapted to be stacked in a solid oxide fuel cell stack. The obtained half......-cell has an improved planar shape, which remains planar also after a sintering process and during temperature fluctuations....

Planar UV excilamp excited by a surface barrier discharge

Energy Technology Data Exchange (ETDEWEB)

Guivan, N N [Department of Quantum Electronics, Uzhgorod National University, Pidgirna 46, Uzhgorod 88000 (Ukraine); Janca, J [Department of Physical Electronics, Masaryk University, Kotlarska 2, Brno 61137 (Czech Republic); Brablec, A [Department of Physical Electronics, Masaryk University, Kotlarska 2, Brno 61137 (Czech Republic); Stahel, P [Department of Physical Electronics, Masaryk University, Kotlarska 2, Brno 61137 (Czech Republic); SlavIcek, P [Department of Physical Electronics, Masaryk University, Kotlarska 2, Brno 61137 (Czech Republic); Shimon, L L [Department of Quantum Electronics, Uzhgorod National University, Pidgirna 46, Uzhgorod 88000 (Ukraine)

2005-09-07

In this paper, the typical characteristics of a planar excilamp based on KrCl* and XeCl* exciplex molecules are presented. The excitation of the working mixture Kr/Xe/Cl{sub 2} is realized by means of the surface barrier discharge at pressures of 0.1-1 bar. The following properties are measured and discussed: spectra emitted by the plasma in the UV/VIS/NIR spectral range, intensity of emitted light versus total pressure in the discharge, the composition of the working mixture and the power of emitted light. The radiation power versus input electric power, and space distribution of the emitted light including basic electrical parameters of the discharge were also measured. It was shown that the characteristic power of UV radiation emitted in the spectral range 200-400 nm is about 6 mW cm{sup -2} while the efficiency could be about 8%.

Piezo Voltage Controlled Planar Hall Effect Devices.

Science.gov (United States)

Zhang, Bao; Meng, Kang-Kang; Yang, Mei-Yin; Edmonds, K W; Zhang, Hao; Cai, Kai-Ming; Sheng, Yu; Zhang, Nan; Ji, Yang; Zhao, Jian-Hua; Zheng, Hou-Zhi; Wang, Kai-You

2016-06-22

The electrical control of the magnetization switching in ferromagnets is highly desired for future spintronic applications. Here we report on hybrid piezoelectric (PZT)/ferromagnetic (Co2FeAl) devices in which the planar Hall voltage in the ferromagnetic layer is tuned solely by piezo voltages. The change of planar Hall voltage is associated with magnetization switching through 90° in the plane under piezo voltages. Room temperature magnetic NOT and NOR gates are demonstrated based on the piezo voltage controlled Co2FeAl planar Hall effect devices without the external magnetic field. Our demonstration may lead to the realization of both information storage and processing using ferromagnetic materials.

Exploring Charge Transport in Guest Molecule Infiltrated Cu₃(BTC)₂ Metal Organic Framework

Energy Technology Data Exchange (ETDEWEB)

Leonard, Francois Leonard [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Stavila, Vitalie [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Allendorf, Mark D. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

2014-09-01

The goal of this Exploratory Express project was to expand the understanding of the physical properties of our recently discovered class of materials consisting of metal-organic frameworks with electroactive ‘guest’ molecules that together form an electrically conducting charge-transfer complex (molecule@MOF). Thin films of Cu₃(BTC)₂ were grown on fused silica using solution step-by-step growth and were infiltrated with the molecule tetracyanoquinodimethane (TCNQ). The infiltrated MOF films were extensively characterized using optical microscopy, scanning electron microscopy, Raman spectroscopy, electrical conductivity, and thermoelectric properties. Thermopower measurements on TCNQ@Cu₃(BTC)₂ revealed a positive Seebeck coefficient of ~400 μV/k, indicating that holes are the primary carriers in this material. The high value of the Seebeck coefficient and the expected low thermal conductivity suggest that molecule@MOF materials may be attractive for thermoelectric power conversion applications requiring low cost, solution-processable, and non-toxic active materials.

Improved efficiency in organic/inorganic hybrid solar cells by interfacial modification of ZnO nanowires with small molecules

International Nuclear Information System (INIS)

Chang, Sehoon; Park, Hyesung; Cheng, Jayce J; Rekemeyer, Paul H; Gradečak, Silvija

2014-01-01

We demonstrate improved photovoltaic performance of ZnO nanowire/poly(3-hexylthiophene) (P3HT) nanofiber hybrid devices using an interfacial modification of ZnO nanowires. Formation of cascade energy levels between the ZnO nanowire and P3HT nanofiber was achieved by interfacial modification of ZnO nanowires using small molecules tetraphenyldibenzoperiflanthene (DBP) and 3,4,9,10-perylenetetracarboxylic bisbenzimidazole (PTCBI). The successful demonstration of improved device performance owing to the cascade energy levels by small molecule modification is a promising approach toward highly efficient organic/inorganic hybrid solar cells. (paper)

Attractive planar panelization using dynamic relaxation principles

NARCIS (Netherlands)

Gauss, Florian; Teuffel, Patrick

2015-01-01

In the presented paper a new method is proposed to approximate a given NURBS surface with a PQ (Planar Quad) mesh. The desired mesh layout will be generated in then attracted to the target surface. The process iteratively pulls the mesh vertices towards the target surface and then planarizes the

Planar Hall effect bridge magnetic field sensors

DEFF Research Database (Denmark)

Henriksen, A.D.; Dalslet, Bjarke Thomas; Skieller, D.H.

2010-01-01

Until now, the planar Hall effect has been studied in samples with cross-shaped Hall geometry. We demonstrate theoretically and experimentally that the planar Hall effect can be observed for an exchange-biased ferromagnetic material in a Wheatstone bridge topology and that the sensor signal can...... Hall effect bridge sensors....

Column Planarity and Partially-Simultaneous Geometric Embedding

Czech Academy of Sciences Publication Activity Database

Barba, L.; Evans, W.; Hoffmann, M.; Kusters, V.; Saumell, Maria; Speckmann, B.

2017-01-01

Roč. 21, č. 6 (2017), s. 983-1002 ISSN 1526-1719 Grant - others:GA MŠk(CZ) LO1506; GA MŠk(CZ) EE2.3.30.0038 Institutional support: RVO:67985807 Keywords : column planarity * unlabeled level planarity * simultaneous geometric embedding Subject RIV: BA - General Mathematics OBOR OECD: Pure mathematics

Pulsed laser planarization of metal films for multilevel interconnects

International Nuclear Information System (INIS)

Tuckerman, D.B.; Schmitt, R.L.

1985-05-01

Multilevel interconnect schemes for integrated circuits generally require one or more planarization steps, in order to maintain an acceptably flat topography for lithography and thin-film step coverage on the higher levels. Traditional approaches have involved planarization of the interlevel insulation (dielectric) layers, either by spin-on application (e.g., polyimide), or by reflow (e.g., phosphosilicate glass). We have pursued an alternative approach, in which each metal level is melted (hence planarized) using a pulsed laser prior to patterning. Short (approx.1 μs) pulses are used to preclude undesirable metallurgical reactions between the film, adhesion or barrier layer, and dielectric layer. Laser planarization of metals is particularly well suited to multilevel systems which include ground or power planes. Results are presented for planarization of gold films on SiO 2 dielectric layers using a flashlamp-pumped dye laser. The pulse duration is approx.1 μs, which allows the heat pulse to uniformly penetrate the gold while not penetrating substantially through the underlying SiO 2 (hence not perturbing the lower levels of metal). Excellent planarization of the gold films is achieved (less than 0.1 μm surface roughness, even starting with extreme topographic variations), as well as improved conductivity. To demonstrate the process, numerous planarized two-layer structures (transmission lines under a ground plane) were fabricated and characterized. 9 refs., 2 figs

Assessment of Density-Functional Tight-Binding Ionization Potentials and Electron Affinities of Molecules of Interest for Organic Solar Cells Against First-Principles GW Calculations

Directory of Open Access Journals (Sweden)

Ala Aldin M. H. M. Darghouth

2015-12-01

Full Text Available Ionization potentials (IPs and electron affinities (EAs are important quantities input into most models for calculating the open-circuit voltage (Voc of organic solar cells. We assess the semi-empirical density-functional tight-binding (DFTB method with the third-order self-consistent charge (SCC correction and the 3ob parameter set (the third-order DFTB (DFTB3 organic and biochemistry parameter set against experiments (for smaller molecules and against first-principles GW (Green’s function, G, times the screened potential, W calculations (for larger molecules of interest in organic electronics for the calculation of IPs and EAs. Since GW calculations are relatively new for molecules of this size, we have also taken care to validate these calculations against experiments. As expected, DFTB is found to behave very much like density-functional theory (DFT, but with some loss of accuracy in predicting IPs and EAs. For small molecules, the best results were found with ΔSCF (Δ self-consistent field SCC-DFTB calculations for first IPs (good to ± 0.649 eV. When considering several IPs of the same molecule, it is convenient to use the negative of the orbital energies (which we refer to as Koopmans’ theorem (KT IPs as an indication of trends. Linear regression analysis shows that KT SCC-DFTB IPs are nearly as accurate as ΔSCF SCC-DFTB eigenvalues (± 0.852 eV for first IPs, but ± 0.706 eV for all of the IPs considered here for small molecules. For larger molecules, SCC-DFTB was also the ideal choice with IP/EA errors of ± 0.489/0.740 eV from ΔSCF calculations and of ± 0.326/0.458 eV from (KT orbital energies. Interestingly, the linear least squares fit for the KT IPs of the larger molecules also proves to have good predictive value for the lower energy KT IPs of smaller molecules, with significant deviations appearing only for IPs of 15–20 eV or larger. We believe that this quantitative analysis of errors in SCC-DFTB IPs and EAs may be of

Planar Cell Polarity Controls Pancreatic Beta Cell Differentiation and Glucose Homeostasis

Directory of Open Access Journals (Sweden)

Cedric Cortijo

2012-12-01

Full Text Available Planar cell polarity (PCP refers to the collective orientation of cells within the epithelial plane. We show that progenitor cells forming the ducts of the embryonic pancreas express PCP proteins and exhibit an active PCP pathway. Planar polarity proteins are acquired at embryonic day 11.5 synchronously to apicobasal polarization of pancreas progenitors. Loss of function of the two PCP core components Celsr2 and Celsr3 shows that they control the differentiation of endocrine cells from polarized progenitors, with a prevalent effect on insulin-producing beta cells. This results in a decreased glucose clearance. Loss of Celsr2 and 3 leads to a reduction of Jun phosphorylation in progenitors, which, in turn, reduces beta cell differentiation from endocrine progenitors. These results highlight the importance of the PCP pathway in cell differentiation in vertebrates. In addition, they reveal that tridimensional organization and collective communication of cells are needed in the pancreatic epithelium in order to generate appropriate numbers of endocrine cells.

Strategy to discover diverse optimal molecules in the small molecule universe.

Science.gov (United States)

Rupakheti, Chetan; Virshup, Aaron; Yang, Weitao; Beratan, David N

2015-03-23

The small molecule universe (SMU) is defined as a set of over 10(60) synthetically feasible organic molecules with molecular weight less than ∼500 Da. Exhaustive enumerations and evaluation of all SMU molecules for the purpose of discovering favorable structures is impossible. We take a stochastic approach and extend the ACSESS framework ( Virshup et al. J. Am. Chem. Soc. 2013 , 135 , 7296 - 7303 ) to develop diversity oriented molecular libraries that can generate a set of compounds that is representative of the small molecule universe and that also biases the library toward favorable physical property values. We show that the approach is efficient compared to exhaustive enumeration and to existing evolutionary algorithms for generating such libraries by testing in the NKp fitness landscape model and in the fully enumerated GDB-9 chemical universe containing 3 × 10(5) molecules.

Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars.

Science.gov (United States)

Rix, Catherine S; Sims, Mark R; Cullen, David C

2011-11-01

The proposed ExoMars mission, due to launch in 2018, aims to look for evidence of extant and extinct life in martian rocks and regolith. Previous attempts to detect organic molecules of biological or abiotic origin on Mars have been unsuccessful, which may be attributable to destruction of these molecules by perchlorate salts during pyrolysis sample extraction techniques. Organic molecules can also be extracted and measured with solvent-based systems. The ExoMars payload includes the Life Marker Chip (LMC) instrument, capable of detecting biomarker molecules of extant and extinct Earth-like life in liquid extracts of martian samples with an antibody microarray assay. The aim of the work reported here was to investigate whether the presence of perchlorate salts, at levels similar to those at the NASA Phoenix landing site, would compromise the LMC extraction and detection method. To test this, we implemented an LMC-representative sample extraction process with an LMC-representative antibody assay and used these to extract and analyze a model sample that consisted of a Mars analog sample matrix (JSC Mars-1) spiked with a representative organic molecular target (pyrene, an example of abiotic meteoritic infall targets) in the presence of perchlorate salts. We found no significant change in immunoassay function when using pyrene standards with added perchlorate salts. When model samples spiked with perchlorate salts were subjected to an LMC-representative liquid extraction, immunoassays functioned in a liquid extract and detected extracted pyrene. For the same model sample matrix without perchlorate salts, we observed anomalous assay signals that coincided with yellow coloration of the extracts. This unexpected observation is being studied further. This initial study indicates that the presence of perchlorate salts, at levels similar to those detected at the NASA Phoenix landing site, is unlikely to prevent the LMC from extracting and detecting organic molecules from

Stabilizing and Organizing Bi3 Cu4 and Bi7 Cu12 Nanoclusters in Two-Dimensional Metal-Organic Networks.

Science.gov (United States)

Yan, Linghao; Xia, Bowen; Zhang, Qiushi; Kuang, Guowen; Xu, Hu; Liu, Jun; Liu, Pei Nian; Lin, Nian

2018-04-16

Multinuclear heterometallic nanoclusters with controllable stoichiometry and structure are anticipated to possess promising catalytic, magnetic, and optical properties. Heterometallic nanoclusters with precise stoichiometry of Bi 3 Cu 4 and Bi 7 Cu 12 can be stabilized in the scaffold of two-dimensional metal-organic networks on a Cu(111) surface through on-surface metallosupramolecular self-assembly processes. The atomic structures of the nanoclusters were resolved using scanning tunneling microscopy and density functional theory calculations. The nanoclusters feature highly symmetric planar hexagonal shapes and core-shell charge modulation. The clusters are arranged as triangular lattices with a periodicity that can be tuned by choosing molecules of different size. This work shows that on-surface metallosupramolecular self-assembly creates unique possibilities for the design and synthesis of multinuclear heterometallic nanoclusters. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale charge localization induced by random orientations of organic molecules in hybrid perovskite CH3NH3PbI3

Science.gov (United States)

Ma, Jie; Wang, Lin-Wang

2015-03-01

Perovskite-based solar cells have achieved high solar-energy conversion efficiencies and attracted wide attentions nowadays. Despite the rapid progress in solar-cell devices, many fundamental issues of the hybrid perovskites have not been fully understood. Experimentally, it is well known that in CH3NH3PbI3, the organic molecules CH3NH3 are randomly orientated at the room temperature, but the impact of the random molecular orientation has not been investigated. Using linear-scaling ab-initiomethods, we have calculated the electronic structures of the tetragonal phase of CH3NH3PbI3 with randomly orientated organic molecules in large supercells up to ~20,000 atoms. Due to the dipole moment of the organic molecule, the random orientation creates a novel system with long-range potential fluctuations unlike alloys or other conventional disordered systems. We find that the charge densities of the conduction-band minimum and the valence-band maximum are localized separately in nanoscales due to the potential fluctuations. The charge localization causes electron-hole separation and reduces carrier recombination rates, which may contribute to the long carrier lifetime observed in experiments. We have also proposed a model to explain the charge localization.

Planar Elongation Measurements on Soft Elastomers

DEFF Research Database (Denmark)

Jensen, Mette Krog; Skov, Anne Ladegaard; Rasmussen, Henrik K.

2009-01-01

A new fixture to the filament stretch rheometer (FSR) has been developed to measure planar elongation of soft polymeric networks. To validate this new technique, soft polymeric networks of poly(propyleneoxide) (PPO) were investigated during deformation.......A new fixture to the filament stretch rheometer (FSR) has been developed to measure planar elongation of soft polymeric networks. To validate this new technique, soft polymeric networks of poly(propyleneoxide) (PPO) were investigated during deformation....

Small molecules as tracers in atmospheric secondary organic aerosol

Science.gov (United States)

Yu, Ge

Secondary organic aerosol (SOA), formed from in-air oxidation of volatile organic compounds, greatly affects human health and climate. Although substantial research has been devoted to SOA formation and evolution, the modeled and lab-generated SOA are still low in mass and degree of oxidation compared to ambient measurements. In order to compensate for these discrepancies, the aqueous processing pathway has been brought to attention. The atmospheric waters serve as aqueous reaction media for dissolved organics to undergo further oxidation, oligomerization, or other functionalization reactions, which decreases the vapor pressure while increasing the oxidation state of carbon atoms. Field evidence for aqueous processing requires the identification of tracer products such as organosulfates. We synthesized the standards for two organosulfates, glycolic acid sulfate and lactic acid sulfate, in order to measure their aerosol-state concentration from five distinct locations via filter samples. The water-extracted filter samples were analyzed by LC-MS. Lactic acid sulfate and glycolic acid sulfate were detected in urban locations in the United States, Mexico City, and Pakistan with varied concentrations, indicating their potential as tracers. We studied the aqueous processing reaction between glyoxal and nitrogen-containing species such as ammonium and amines exclusively by NMR spectrometry. The reaction products formic acid and several imidazoles along with the quantified kinetics were reported. The brown carbon generated from these reactions were quantified optically by UV-Vis spectroscopy. The organic-phase reaction between oxygen molecule and alkenes photosensitized by alpha-dicarbonyls were studied in the same manner. We observed the fast kinetics transferring alkenes to epoxides under simulated sunlight. Statistical estimations indicate a very effective conversion of aerosol-phase alkenes to epoxides, potentially forming organosulfates in a deliquescence event and

Planar metasurface retroreflector

Science.gov (United States)

Arbabi, Amir; Arbabi, Ehsan; Horie, Yu; Kamali, Seyedeh Mahsa; Faraon, Andrei

2017-07-01

Metasurfaces are two-dimensional arrangements of subwavelength scatterers that control the propagation of optical waves. Here, we show that cascaded metasurfaces, each performing a predefined mathematical transformation, provide a new optical design framework that enables new functionalities not yet demonstrated with single metasurfaces. Specifically, we demonstrate that retroreflection can be achieved with two vertically stacked planar metasurfaces, the first performing a spatial Fourier transform and its inverse, and the second imparting a spatially varying momentum to the Fourier transform of the incident light. Using this concept, we fabricate and test a planar monolithic near-infrared retroreflector composed of two layers of silicon nanoposts, which reflects light along its incident direction with a normal incidence efficiency of 78% and a large half-power field of view of 60°. The metasurface retroreflector demonstrates the potential of cascaded metasurfaces for implementing novel high-performance components, and enables low-power and low-weight passive optical transmitters.

The synthesis and properties of linear A-π-D-π-A type organic small molecule containing diketopyrrolopyrrole terminal units

Science.gov (United States)

Zhang, Shanshan; Niu, Qingfen; Sun, Tao; Li, Yang; Li, Tianduo; Liu, Haixia

2017-08-01

A novel linear A-π-D-π-A-type organic small molecule Ph2(PDPP)2 consisting diketopyrrolopyrrole (DPP) as acceptor unit, biphenylene as donor unit and acetylene unit as π-linkage has been successfully designed and synthesized. Its corresponding thermal, photophysical and electrochemical properties as well as the photoinduced charge-separation process were investigated. Ph2(PDPP)2 exhibits high thermal stability and it can be soluble in common organic solvents such as chloroform and tetrahydrofuran. The photophysical properties show that DPP2Ph2 harvests sunlight over the entire visible spectrum range in the thin-film state (300-800 nm). DPP2Ph2 has lower band gaps and appropriate energy levels to satisfy the requirement of solution-processable organic solar cells. The efficient photoinduced charge separation process was clearly observed between DPP2Ph2 with PC61BM and the Ksv value was found to be as high as 2.13 × 104 M- 1. Therefore, these excellent properties demonstrate that the designed A-π-D-π-A-type small molecule Ph2(PDPP)2 is the prospective candidate as donor material for organic photovoltaic material.

Chaotic non-planar vibrations of the thin elastica. Part I: Experimental observation of planar instability

Science.gov (United States)

Cusumano, J. P.; Moon, F. C.

1995-01-01

In this two-part paper, the results of an investigation into the non-linear dynamics of a flexible cantilevered rod (the elastica) with a thin rectangular cross-section are presented. An experimental examination of the dynamics of the elastica over a broad parameter range forms the core of Part I. In Part II, the experimental work is related to a theoretical study of the mechanics of the elastica, and the study of a two-degree-of-freedom model obtained by modal projection. The experimental system used in this investigation is a rod with clamped-free boundary conditions, forced by sinusoidally displacing the clamped end. Planar periodic motions of the driven elastica are shown to lose stability at distinct resonant wedges, and the resulting motions are shown in general to be non-planar, chaotic, bending-torsion oscillations. Non-planar motions in all resonances exhibit energy cascading and dynamic two-well phenomena, and a family of asymmetric, bending-torsion non-linear modes is discovered. Correlation dimension calculations are used to estimate the number of active degrees of freedom in the system.

OLED Fabrication by Using a Novel Planar Evaporation Technique

Directory of Open Access Journals (Sweden)

Fu-Ching Tung

2014-01-01

Full Text Available Organic light-emitting diode fabrication is suffering from extremely high material wasting during deposition especially using a typical point or even line source. Moreover, the need of depositing a high number of emitters and host(s with a precise composition control in a single layer makes traditional vapor codeposition systems nearly impossible, unless otherwise with a very low yield. To improve, we have developed a novel thin-film deposition system with a planar source loadable with any premetered solvent-mixed organic compounds, plausibly with no component number limitation. We hence demonstrate experimentally, along with a Monte Carlo simulation, in the report the feasibility of using the technique to deposit on a large area-size substrate various organic materials with a relatively high material utilization rate coupling with high film uniformity. Specifically, nonuniformity of less than ±5% and material utilization rate of greater than 70% have been obtained for the studied films.

Computational Study on a PTAS for Planar Dominating Set Problem

Directory of Open Access Journals (Sweden)

Qian-Ping Gu

2013-01-01

Full Text Available The dominating set problem is a core NP-hard problem in combinatorial optimization and graph theory, and has many important applications. Baker [JACM 41,1994] introduces a k-outer planar graph decomposition-based framework for designing polynomial time approximation scheme (PTAS for a class of NP-hard problems in planar graphs. It is mentioned that the framework can be applied to obtain an O(2ckn time, c is a constant, (1+1/k-approximation algorithm for the planar dominating set problem. We show that the approximation ratio achieved by the mentioned application of the framework is not bounded by any constant for the planar dominating set problem. We modify the application of the framework to give a PTAS for the planar dominating set problem. With k-outer planar graph decompositions, the modified PTAS has an approximation ratio (1 + 2/k. Using 2k-outer planar graph decompositions, the modified PTAS achieves the approximation ratio (1+1/k in O(22ckn time. We report a computational study on the modified PTAS. Our results show that the modified PTAS is practical.

Belief propagation and loop series on planar graphs

International Nuclear Information System (INIS)

Chertkov, Michael; Teodorescu, Razvan; Chernyak, Vladimir Y

2008-01-01

We discuss a generic model of Bayesian inference with binary variables defined on edges of a planar graph. The Loop Calculus approach of Chertkov and Chernyak (2006 Phys. Rev. E 73 065102(R) [cond-mat/0601487]; 2006 J. Stat. Mech. P06009 [cond-mat/0603189]) is used to evaluate the resulting series expansion for the partition function. We show that, for planar graphs, truncating the series at single-connected loops reduces, via a map reminiscent of the Fisher transformation (Fisher 1961 Phys. Rev. 124 1664), to evaluating the partition function of the dimer-matching model on an auxiliary planar graph. Thus, the truncated series can be easily re-summed, using the Pfaffian formula of Kasteleyn (1961 Physics 27 1209). This allows us to identify a big class of computationally tractable planar models reducible to a dimer model via the Belief Propagation (gauge) transformation. The Pfaffian representation can also be extended to the full Loop Series, in which case the expansion becomes a sum of Pfaffian contributions, each associated with dimer matchings on an extension to a subgraph of the original graph. Algorithmic consequences of the Pfaffian representation, as well as relations to quantum and non-planar models, are discussed

Optical study of planar waveguides based on oxidized porous silicon impregnated with laser dyes

Energy Technology Data Exchange (ETDEWEB)

Chouket, A. [Unite de recherche de Spectroscopie Raman, Departement de Physique, Faculte des Sciences de Tunis, Elmanar 2092, Tunis (Tunisia); Charrier, J. [Laboratoire d' Optronique CNRS-UMR FOTON 6082, Universite de Rennes 1, ENSSAT-6 rue de Kerampont, BP 80518, 22305 Lannion Cedex (France); Elhouichet, H. [Unite de recherche de Spectroscopie Raman, Departement de Physique, Faculte des Sciences de Tunis, Elmanar 2092, Tunis (Tunisia)], E-mail: habib.elhouichet@fst.rnu.tn; Oueslati, M. [Unite de recherche de Spectroscopie Raman, Departement de Physique, Faculte des Sciences de Tunis, Elmanar 2092, Tunis (Tunisia)

2009-05-15

Oxidized porous silicon optical planar waveguides were elaborated and impregnated with rhodamine B and rhodamine 6G. The waveguiding, absorption, and photoluminescence properties of these impregnated waveguides were studied. Successful impregnation of the structure with laser dyes is shown from photoluminescence and reflectivity measurements. Furthermore, the reflectivity spectra prove the homogenous incorporation of both dye molecules inside the pores of the matrices. The refractive indices of waveguide layers were determined before and after dye impregnation to indicate the conservation of guiding conditions. The optical losses in the visible wavelengths are studied as a function of dye concentration. The dye absorption is the main reason for these losses.

The Identification of Complex Organic Molecules in the Interstellar Medium: Using Lasers and Matrix Isolation Spectroscopy to Simulate the Interstellar Environment

Science.gov (United States)

Stone, Bradley M.

1998-01-01

The Astrochemistry Group at NASA Ames Research Center is interested in the identification of large organic molecules in the interstellar medium Many smaller organic species (e.g. hydrocarbons, alcohols, etc.) have been previously identified by their radiofrequency signature due to molecular rotations. However, this becomes increasingly difficult to observe as the size of the molecule increases. Our group in interested in the identification of the carriers of the Diffuse Interstellar Bands (absorption features observed throughout the visible and near-infrared in the spectra of stars, due to species in the interstellar medium). Polycyclic Aromatic Hydrocarbons (PAHs) and related molecules are thought to be good candidates for these carriers. Laboratory experiments am performed at Ames to simulate the interstellar environment, and to compare spectra obtained from molecules in the laboratory to those derived astronomically. We are also interested in PAHs with respect to their possible connection to the UIR (Unidentified infrared) and ERE (Extended Red Emission) bands - emission features found to emanate from particular regions of our galaxy (e.g. Orion nebula, Red Rectangle, etc.). An old, "tried and proven spectroscopic technique, matrix isolation spectroscopy creates molecular conditions ideal for performing laboratory astrophysics.

A Research Module for the Organic Chemistry Laboratory: Multistep Synthesis of a Fluorous Dye Molecule.

Science.gov (United States)

Slade, Michael C; Raker, Jeffrey R; Kobilka, Brandon; Pohl, Nicola L B

2014-01-14

A multi-session research-like module has been developed for use in the undergraduate organic teaching laboratory curriculum. Students are tasked with planning and executing the synthesis of a novel fluorous dye molecule and using it to explore a fluorous affinity chromatography separation technique, which is the first implementation of this technique in a teaching laboratory. Key elements of the project include gradually introducing students to the use of the chemical literature to facilitate their searching, as well as deliberate constraints designed to force them to think critically about reaction design and optimization in organic chemistry. The project also introduces students to some advanced laboratory practices such as Schlenk techniques, degassing of reaction mixtures, affinity chromatography, and microwave-assisted chemistry. This provides students a teaching laboratory experience that closely mirrors authentic synthetic organic chemistry practice in laboratories throughout the world.

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

Science.gov (United States)

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 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.

Excitonic Coupling in Linear and Trefoil Trimer Perylenediimide Molecules Probed by Single-Molecule Spectroscopy

KAUST Repository

Yoo, Hyejin

2012-10-25

Perylenediimide (PDI) molecules are promising building blocks for photophysical studies of electronic interactions within multichromophore arrays. Such PDI arrays are important materials for fabrication of molecular nanodevices such as organic light-emitting diodes, organic semiconductors, and biosensors because of their high photostability, chemical and physical inertness, electron affinity, and high tinctorial strength over the entire visible spectrum. In this work, PDIs have been organized into linear (L3) and trefoil (T3) trimer molecules and investigated by single-molecule fluorescence microscopy to probe the relationship between molecular structures and interchromophoric electronic interactions. We found a broad distribution of coupling strengths in both L3 and T3 and hence strong/weak coupling between PDI units by monitoring spectral peak shifts in single-molecule fluorescence spectra upon sequential photobleaching of each constituent chromophore. In addition, we used a wide-field defocused imaging technique to resolve heterogeneities in molecular structures of L3 and T3 embedded in a PMMA polymer matrix. A systematic comparison between the two sets of experimental results allowed us to infer the correlation between intermolecular interactions and molecular structures. Our results show control of the PDI intermolecular interactions using suitable multichromophoric structures. © 2012 American Chemical Society.

Excitonic Coupling in Linear and Trefoil Trimer Perylenediimide Molecules Probed by Single-Molecule Spectroscopy

KAUST Repository

Yoo, Hyejin; Furumaki, Shu; Yang, Jaesung; Lee, Ji-Eun; Chung, Heejae; Oba, Tatsuya; Kobayashi, Hiroyuki; Rybtchinski, Boris; Wilson, Thea M.; Wasielewski, Michael R.; Vacha, Martin; Kim, Dongho

2012-01-01

Perylenediimide (PDI) molecules are promising building blocks for photophysical studies of electronic interactions within multichromophore arrays. Such PDI arrays are important materials for fabrication of molecular nanodevices such as organic light-emitting diodes, organic semiconductors, and biosensors because of their high photostability, chemical and physical inertness, electron affinity, and high tinctorial strength over the entire visible spectrum. In this work, PDIs have been organized into linear (L3) and trefoil (T3) trimer molecules and investigated by single-molecule fluorescence microscopy to probe the relationship between molecular structures and interchromophoric electronic interactions. We found a broad distribution of coupling strengths in both L3 and T3 and hence strong/weak coupling between PDI units by monitoring spectral peak shifts in single-molecule fluorescence spectra upon sequential photobleaching of each constituent chromophore. In addition, we used a wide-field defocused imaging technique to resolve heterogeneities in molecular structures of L3 and T3 embedded in a PMMA polymer matrix. A systematic comparison between the two sets of experimental results allowed us to infer the correlation between intermolecular interactions and molecular structures. Our results show control of the PDI intermolecular interactions using suitable multichromophoric structures. © 2012 American Chemical Society.

Planar quantum squeezing and atom interferometry

Energy Technology Data Exchange (ETDEWEB)

He, Q. Y.; Drummond, P. D.; Reid, M. D. [ARC Centre of Excellence for Quantum-Atom Optics, Centre for Atom Optics and Ultrafast Spectroscopy, Swinburne University of Technology, Melbourne 3122 (Australia); Peng Shiguo [Department of Physics, Tsinghua University, Beijing 100084 (China)

2011-08-15

We obtain a lower bound on the sum of two orthogonal spin component variances in a plane. This gives a planar uncertainty relation which holds even when the Heisenberg relation is not useful. We investigate the asymptotic, large-J limit and derive the properties of the planar quantum squeezed states that saturate this uncertainty relation. These states extend the concept of spin squeezing to any two conjugate spin directions. We show that planar quantum squeezing can be achieved experimentally as the ground state of a Bose-Einstein condensate in two coupled potential wells with a critical attractive interaction. These states reduce interferometric phase noise at all phase angles simultaneously. This is useful for one-shot interferometric phase measurements where the measured phase is completely unknown. Our results can also be used to derive entanglement criteria for multiple spins J at separated sites, with applications in quantum information.

Searching for planar signatures in WMAP

International Nuclear Information System (INIS)

Abramo, L. Raul; Bernui, Armando; Pereira, Thiago S.

2009-01-01

We search for planar deviations of statistical isotropy in the Wilkinson Microwave Anisotropy Probe (WMAP) data by applying a recently introduced angular-planar statistics both to full-sky and to masked temperature maps, including in our analysis the effect of the residual foreground contamination and systematics in the foreground removing process as sources of error. We confirm earlier findings that full-sky maps exhibit anomalies at the planar (l) and angular (l) scales (l,l) = (2,5),(4,7), and (6,8), which seem to be due to unremoved foregrounds since this features are present in the full-sky map but not in the masked maps. On the other hand, our test detects slightly anomalous results at the scales (l,l) = (10,8) and (2,9) in the masked maps but not in the full-sky one, indicating that the foreground cleaning procedure (used to generate the full-sky map) could not only be creating false anomalies but also hiding existing ones. We also find a significant trace of an anomaly in the full-sky map at the scale (l,l) = (10,5), which is still present when we consider galactic cuts of 18.3% and 28.4%. As regards the quadrupole (l = 2), we find a coherent over-modulation over the whole celestial sphere, for all full-sky and cut-sky maps. Overall, our results seem to indicate that current CMB maps derived from WMAP data do not show significant signs of anisotropies, as measured by our angular-planar estimator. However, we have detected a curious coherence of planar modulations at angular scales of the order of the galaxy's plane, which may be an indication of residual contaminations in the full- and cut-sky maps

Spatial and temporal superresolution concepts to study plasma membrane organization by single molecule fluorescence techniques

International Nuclear Information System (INIS)

Ruprecht, V.

2010-01-01

Fluorescence microscopy techniques are currently among the most important experimental tools to study cellular processes. Ultra-sensitive detection devices nowadays allow for measuring even individual farnesylacetate labeled target molecules with nanometer spatial accuracy and millisecond time resolution. The emergence of single molecule fluorescence techniques especially contributed to the field of membrane biology and provided basic knowledge on structural and dynamic features of the cellular plasma membrane. However, we are still confronted with a rather fragmentary understanding of the complex architecture and functional interrelations of membrane constituents. In this thesis new concepts in one- and dual-color single molecule fluorescence techniques are presented that allow for addressing organization principles and interaction dynamics in the live cell plasma membrane. Two complementary experimental strategies are described which differ in their detection principle: single molecule fluorescence imaging and fluorescence correlation spectroscopy. The presented methods are discussed in terms of their implementation, accuracy, quantitative and statistical data analysis, as well as live cell applications. State-of-the-art dual color single molecule imaging is introduced as the most direct experimental approach to study interaction dynamics between differently labeled target molecules. New analytical estimates for robust data analysis are presented that facilitate quantitative recording and identification of co localizations in dual color single molecule images. A novel dual color illumination scheme is further described that profoundly extends the current range and sensitivity of conventional dual color single molecule experiments. The method enables working at high surface densities of fluorescent molecules - a feature typically incommensurable with single molecule imaging - and is especially suited for the detection of rare interactions by tracking co localized

Substrate and coating defect planarization strategies for high-laser-fluence multilayer mirrors

International Nuclear Information System (INIS)

Stolz, Christopher J.; Wolfe, Justin E.; Mirkarimi, Paul B.; Folta, James A.; Adams, John J.; Menor, Marlon G.; Teslich, Nick E.; Soufli, Regina; Menoni, Carmen S.; Patel, Dinesh

2015-01-01

Planarizing or smoothing over nodular defects in multilayer mirrors can be accomplished by a discrete deposit-and-etch process that exploits the angle-dependent etching rate of optical materials. Typically, nodular defects limit the fluence on mirrors irradiated at 1064 nm with 10 ns pulse lengths due to geometrically- and interference-induced light intensification. Planarized hafina/silica multilayer mirrors have demonstrated > 125 J/cm 2 laser resistance for single-shot testing and 50 J/cm 2 for multi-shot testing for nodular defects originating on the substrate surface. Two planarization methods were explored: thick planarization layers on the substrate surface and planarized silica layers throughout the multilayer in which only the silica layers that are below one half of the incoming electric field value are etched. This paper also describes the impact of planarized defects that are buried within the multilayer structure compared to planarized substrate particulate defects. - Highlights: • Defect planarization significantly improves multilayer mirror laser resistance • Substrate and coating defects have both been effectively planarized • Single and multishot laser resistance improvement was demonstrated

Ultraweak azimuthal anchoring of a nematic liquid crystal on a planar orienting photopolymer

International Nuclear Information System (INIS)

Nespoulous, Mathieu; Blanc, Christophe; Nobili, Maurizio

2007-01-01

The search of weak anchoring is an important issue for a whole class of liquid crystal displays. In this paper we present an orienting layer showing unreached weak planar azimuthal anchoring for 4-n-pentyl-4 ' -cyanobiphenyl nematic liquid crystal (5CB). Azimuthal extrapolation lengths as large as 80 μm are easily obtained. Our layers are made with the commercial photocurable polymer Norland optical adhesive 60. The anisotropy of the film is induced by the adsorption of oriented liquid crystal molecules under a 2 T magnetic field applied parallel to the surfaces. We use the width of surface π-walls and a high-field electro-optical method to measure, respectively, the azimuthal and the zenithal anchorings. The azimuthal anchoring is extremely sensitive to the ultraviolet (UV) dose and it also depends on the magnetic field application duration. On the opposite, the zenithal anchoring is only slightly sensitive to the preparation parameters. All these results are discussed in terms of the adsorption/desorption mechanisms of the liquid crystal molecules on the polymer layer and of the flexibility of the polymer network

Results of the First Mars Organic Molecule Analyzer (MOMA) GC-MS Coupling

Science.gov (United States)

Buch, Arnaud; Pinnick, Veronica; Szopa, Cyril; Danell, Ryan; Grand, Noel; Van Amerom, Friso; Glavin, Daniel; Freissinet, Caroline; Humeau, Olivier; Coll, Patrice; Arevalo, Ricardo; Stalport, Fabien; Brinckerhoff, William; Steininger, Harald; Goesmann, Fred; Mahaffy, Paul; Raulin, Francois

2014-11-01

The Mars Organic Molecule Analyzer (MOMA) aboard the ExoMars rover will be a key analytical tool in providing chemical (molecular) information from the solid samples collected by the rover, with a particular focus on the char-acterization of the organic content. The core of the MOMA instrument is a gas chromatograph coupled with a mass spectrometer (GC-MS) which provides the unique capability to characterize a broad range of compounds, including both of volatile and non-volatile species. Samples will be crushed and deposited into sample cups seated in a rotating carousel. Soil samples will be analyzed either by UV laser desorption / ionization (LDI) or pyrolysis gas chromatography ion trap mass spectrometry (pyr-GC-ITMS).The French GC brassboard was coupled to the US ion trap mass spectrometer brassboard in a flight-like con-figuration for several coupling campains. The MOMA GC setup is based on the SAM heritage design with a He reservoir and 4 separate analytical modules including traps, columns and Thermal Conductivity Detectors. Solid samples are sealed and heated in this setup using a manual tapping station, designed and built at MPS in Germany, for GC-MS analysis. The gaseous species eluting from the GC are then ionized by an electron impact ionization source in the MS chamber and analyzed by the linear ion trap mass spectrometer. Volatile and non-volatile compounds were injected in the MOMA instrumental suite. Both of these compounds classes were detected by the TCD and by the MS. MS signal (total ion current) and single mass spectra by comparison with the NIST library, gave us an unambiguous confirmation of these identifications. The mass spectra arise from an average of 10 mass spectra averaged around a given time point in the total ion chromatogram.Based on commercial instrument, the MOMA requirement for sensitivity in the GC-MS mode for organic molecules is 1 pmol. In this test, sensitivity was determined for the GC TCD and MS response to a dilution

The hyaluronan and proteoglycan link proteins: Organizers of the brain extracellular matrix and key molecules for neuronal function and plasticity.

Science.gov (United States)

Oohashi, Toshitaka; Edamatsu, Midori; Bekku, Yoko; Carulli, Daniela

2015-12-01

The hyaluronan and proteoglycanbinding link protein (Hapln) is a key molecule in the formation and control of hyaluronan-based condensed perineuronal matrix in the adult brain. This review summarizes the recent advances in understanding the role of Haplns in the formation and control of two distinct types of perineuronal matrices, one for "classical" PNN and the other for the specialized extracellular matrix (ECM) at the node of Ranvier in the central nervous system (CNS). We introduce the structural components of each ECM organization including the basic concept of supramolecular structure named "HLT model". We furthermore summarize the developmental and physiological role of perineuronal ECMs from the studies of Haplns and related molecules. Finally, we also discuss the potential mechanism modulating PNNs in the adult CNS. This layer of organized matrices may exert a direct effect via core protein or sugar moiety from the structure or by acting as a binding site for biologically active molecules, which are important for neuronal plasticity and saltatory conduction. Copyright © 2015 Elsevier Inc. All rights reserved.

Singlet oxygen: photosensitized generation, detection and reaction with organic molecules

Energy Technology Data Exchange (ETDEWEB)

Barik, Atanu; Indira Priyadarsini, K; Mohan, Hari; Bajaj, P N; Sapre, A V; Mittal, J P; Mukherjee, T [Radiation and Photochemistry Div., Bhabha Atomic Research Centre, Mumbai (India)

2006-10-15

Singlet molecular oxygen ({sup 1}O{sub 2}) is an excited state of molecular oxygen, having antiparallel spin in the same {pi} antibonding orbital. The study of singlet oxygen production and reactivity has emerged as a rich and diverse area, with implication in diverse fields, such as synthetic chemistry, polymer chemistry, photodynamic therapy, etc. There are several known methods to produce singlet oxygen, and also various techniques employed to detect it. Out of these, photosensitization method is the most popular one. In this article, photosensitized production of singlet oxygen from triplet oxygen and photosensitizers in presence of light, and its detection by the infrared luminescence at 1270 nm have been presented. Further, some results using different types of photosensitizers, effect of solvent on singlet oxygen quantum yields and lifetime have been discussed. The quenching rate constants of singlet oxygen have been determined with different types of organic molecules such as derivatives of thiourea and its analogues, hydroxy indoles and antioxidants and the results have been presented. (author)

Singlet oxygen: photosensitized generation, detection and reaction with organic molecules

International Nuclear Information System (INIS)

Barik, Atanu; Indira Priyadarsini, K.; Hari Mohan; Bajaj, P.N.; Sapre, A.V.; Mittal, J.P.; Mukherjee, T.

2006-10-01

Singlet molecular oxygen ( 1 O 2 ) is an excited state of molecular oxygen, having antiparallel spin in the same π antibonding orbital. The study of singlet oxygen production and reactivity has emerged as a rich and diverse area, with implication in diverse fields, such as synthetic chemistry, polymer chemistry, photodynamic therapy, etc. There are several known methods to produce singlet oxygen, and also various techniques employed to detect it. Out of these, photosensitization method is the most popular one. In this article, photosensitized production of singlet oxygen from triplet oxygen and photosensitizers in presence of light, and its detection by the infrared luminescence at 1270 nm have been presented. Further, some results using different types of photosensitizers, effect of solvent on singlet oxygen quantum yields and lifetime have been discussed. The quenching rate constants of singlet oxygen have been determined with different types of organic molecules such as derivatives of thiourea and its analogues, hydroxy indoles and antioxidants and the results have been presented. (author)

Functionalized organic semiconductor molecules to enhance charge carrier injection in electroluminescent cell

Science.gov (United States)

Yalcin, Eyyup; Kara, Duygu Akin; Karakaya, Caner; Yigit, Mesude Zeliha; Havare, Ali Kemal; Can, Mustafa; Tozlu, Cem; Demic, Serafettin; Kus, Mahmut; Aboulouard, Abdelkhalk

2017-07-01

Organic semiconductor (OSC) materials as a charge carrier interface play an important role to improve the device performance of organic electroluminescent cells. In this study, 4,4″-bis(diphenyl amino)-1,1':3‧,1″-terphenyl-5'-carboxylic acid (TPA) and 4,4″-di-9H-carbazol-9-yl-1,1':3‧,1″-terphenyl-5'-carboxylic acid (CAR) has been designed and synthesized to modify indium tin oxide (ITO) layer as interface. Bare ITO and PEDOT:PSS coated on ITO was used as reference anode electrodes for comparison. Furthermore, PEDOT:PSS coated over CAR/ITO and TPA/ITO to observe stability of OSC molecules and to completely cover the ITO surface. Electrical, optical and surface characterizations were performed for each device. Almost all modified devices showed around 36% decrease at the turn on voltage with respect to bare ITO. The current density of bare ITO, ITO/CAR and ITO/TPA were measured as 288, 1525 and 1869 A/m2, respectively. By increasing current density, luminance of modified devices showed much better performance with respect to unmodified devices.

Selectivity of primary events in the radiation chemistry of organic solids and polymers as revealed by model studies of ionized molecules

International Nuclear Information System (INIS)

Feldman, V.

2006-01-01

Selectivity of the primary chemical events induced by ionizing radiation in molecular systems is the key issue of basic radiation chemistry, which is crucially important for controlling the radiation sensitivity of various-type organic and polymeric materials and designing new effective approaches to the radiation modification. In the past decade we have demonstrated that many features of selective localization of the radiation-induced effects in molecular solids can be understood on the basis of model studies of the primary ionized molecules in rigid low-temperature matrices. This talk will outline the key results of these studies and possible implications for radiation chemistry of vatious systems. In particular, the following aspects will be considered: (1) Spectroscopic characteristics of ustable ionized molecules in low-temperature matrices and their correlations with the site-selective reactivity. (2) Experimental modeling of the effect of excess energy on the properties of primary ionized molecules in condensed phases. (3) Intramolecular long-range effects with particular impact on the properties of ionized bifunctional molecules of X-(CH 2 ) n -X and X-(CH 2 ) n -Y types. (4) Modeling of intermolecular long-range positive hole transfer between molecular traps with close ionization energy and manifestations of 'fine tuning' effects resulting from conformation variations and intermolecular interactions. Several illustrative examples of correlation between the properties of primary ionized molecules and selectivity of the radiation-chemical transformations in organic solids and macromolecules will be presented. Finally, the problem of prediction of the radiation-chemical behaviour of complex organic systems on the basis of limited spectroscopic information and quantum-chemical data obtained for model systems will be addressed. This work was supported by the Russian Foundation for Basic Research (Project No. 06-03-33104) and the Russian Academy of Sciences

Hierarchical organization in aggregates of protein molecules

DEFF Research Database (Denmark)

Bohr, Henrik; Kyhle, Anders; Sørensen, Alexis Hammer

1997-01-01

of the solution and the density of protein are varied shows the existence of specific growth processes resulting in different branch-like structures. The resulting structures are strongly influenced by the shape of each protein molecule. Lysozyme and ribonuclease are found to form spherical structures...

Effect of molecular structure on fragmentation of isolated organic molecules in solid rare gas matrices

International Nuclear Information System (INIS)

Kobrazenko, A.V.; Sukhov, F.F.; Orlov, A.Yu.; Kovalev, G.V.; Baranova, I.A.; Feldman, V.I.

2011-01-01

Complete text of publication follows. Elucidation of high-energy reaction pathways in the condensed phase is an important issue for basic understanding of the radiation stability of complex organic molecules. As was shown previously, organic radical cations (RC) may undergo fragmentation or rearrangement in solid matrices due to excess energy. The probability of this process depends on both ionization potential (IP) of the molecule and molecular structure. In the present work we have studied the role of 'hot' ionic reaction channels for RC of some bifunctional compounds and alkynes. The effect of excess energy was simulated by matrix isolation method as described in detail earlier. The formation of fragmentation products was monitored by EPR and FTIR spectroscopy. In the present work it was shown that the RC of bifunctional compounds (CH 3 OCH 2 COCH 3 , CH 3 CO(CH 2 ) n COCH 3 , n 0/2) dissociated efficiently producing · CH 3 radicals upon irradiation in solid argon matrix at T ≤ 16 K. The probability of fragmentation decreases with decrease of excess energy by switching from Ar to Xe. It is worth noting that acetone RC does not show fragmentation under these conditions. Thus, bifunctional molecules were found to be less stable to 'hot' ionic fragmentation in low-temperature solids in comparison with simple prototype carbonyl compounds. In the case of alkynes of the R-C ≡ CH type, a noticeable yield of fragmentation products was observed when R = -C(CH 3 ) 3 , but it was negligible for R = -CH 3 . It means that the presence of triple bond stabilizes the molecular skeleton of linear alkynes toward 'hot' fragmentation, similarly as it was shown for alkenes. The mechanisms of 'hot' reactions and excess energy relaxation are discussed. This work was supported by the Russian Foundation for Basic Research (project 09-03-00848a).

Beyond level planarity

NARCIS (Netherlands)

Angelini, P.; Da Lozzo, G.; Di Battista, G.; Frati, F.; Patrignani, M.; Rutter, I.; Hu, Y.; Nöllenburg, M.

2016-01-01

In this paper we settle the computational complexity of two open problems related to the extension of the notion of level planarity to surfaces different from the plane. Namely, we show that the problems of testing the existence of a level embedding of a level graph on the surface of the rolling

Versatile piezoelectric pulsed molecular beam source for gaseous compounds and organic molecules with femtomole accuracy for UHV and surface science applications

International Nuclear Information System (INIS)

Schiesser, Alexander; Schaefer, Rolf

2009-01-01

This note describes the construction of a piezoelectric pulsed molecular beam source based upon a design presented in an earlier work [D. Proch and T. Trickl, Rev. Sci. Instrum. 60, 713 (1988)]. The design features significant modifications that permit the determination of the number of molecules in a beam pulse with an accuracy of 1x10 11 molecules per pulse. The 21 cm long plunger-nozzle setup allows the molecules to be brought to any point of the UHV chamber with very high intensity. Furthermore, besides typical gaseous compounds, also smaller organic molecules with a vapor pressure higher than 0.1 mbar at room temperature may serve as feed material. This makes the new design suitable for various applications in chemical and surface science studies.

Response Characterization of a Fiber Optic Sensor Array with Dye-Coated Planar Waveguide for Detection of Volatile Organic Compounds

Directory of Open Access Journals (Sweden)

Jae-Sung Lee

2014-07-01

Full Text Available We have developed a multi-array side-polished optical-fiber gas sensor for the detection of volatile organic compound (VOC gases. The side-polished optical-fiber coupled with a polymer planar waveguide (PWG provides high sensitivity to alterations in refractive index. The PWG was fabricated by coating a solvatochromic dye with poly(vinylpyrrolidone. To confirm the effectiveness of the sensor, five different sensing membranes were fabricated by coating the side-polished optical-fiber using the solvatochromic dyes Reinhardt’s dye, Nile red, 4-aminophthalimide, 4-amino-N-methylphthalimide, and 4-(dimethylaminocinnamaldehyde, which have different polarities that cause changes in the effective refractive index of the sensing membrane owing to evanescent field coupling. The fabricated gas detection system was tested with five types of VOC gases, namely acetic acid, benzene, dimethylamine, ethanol, and toluene at concentrations of 1, 2,…,10 ppb. Second-regression and principal component analyses showed that the response properties of the proposed VOC gas sensor were linearly shifted bathochromically, and each gas showed different response characteristics.

Organic molecules in the polar ice: from chemical analysis to environmental proxies

Science.gov (United States)

Barbante, Carlo; Zennaro, Piero; Giorio, Chiara; Kehrwald, Natalie; Benton, Alisa K.; Wolff, Eric W.; Kalberer, Markus; Kirchgeorg, Torben; Zangrando, Roberta; Barbaro, Elena; Gambaro, Andrea

2015-04-01

The molecular and isotopic compositions of organic matter buried in ice contains information that helps reconstruct past environmental conditions, evaluate histories of climate change, and assess impacts of humans on ecosystems. In recent years novel analytical techniques were developed to quantify molecular compounds in ice cores. As an example, biomass burning markers, including monosaccharide anhydrides, lightweight carboxylic acids, lignin and resin pyrolysis products, black carbon, and charcoal records help in reconstructing past fire activity across seasonal to millennial time scales. Terrestrial biomarkers, such as plant waxes (e.g. long-chain n-alkanes) are also a promising paleo vegetation proxy in ice core studies. Polycyclic aromatic hydrocarbons are ubiquitous pollutants recently detected in ice cores. These hydrocarbons primarily originate from incomplete combustion of organic matter and fossil fuels (e.g. diesel engines, domestic heating, industrial combustion) and therefore can be tracers of past combustion activities. In order to be suitable for paloeclimate purposes, organic molecular markers detected in ice cores should include the following important features. Markers have to be stable under oxidizing atmospheric conditions, and ideally should not react with hydroxyl radicals, during their transport to polar regions. Organic markers must be released in large amounts in order to be detected at remote distances from the sources. Proxies must be specific, in order to differentiate them from other markers with multiple sources. The extraction of glaciochemical information from ice cores is challenging due to the low concentrations of some impurities, thereby demanding rigorous control of external contamination sources and sensitive analytical techniques. Here, we review the analysis and use of organic molecules in ice as proxies of important environmental and climatic processes.

Evaluation of cardiac function using multi-shot echo planar imaging

Energy Technology Data Exchange (ETDEWEB)

Nakanishi, Tadashi; Tanitame, Nobuko; Hata, Ryoichiro; Hirai, Nobuhiko; Ikeda, Midori; Ono, Chiaki; Fukuoka, Haruhito; Ito, Katsuhide [Hiroshima Univ. (Japan). School of Medicine

1998-01-01

In this study, we performed multi-shot echo planar imaging (8 shot, TR/TE/FL=55 ms/18 ms/60 degrees) and k-space segmented fast gradient echo sequence (8 views per segment, TR/TE/FL=9.9 ms/1.8 ms/30 degrees) to assess cardiac function in healthy volunteers. Transaxial sections of the entire heart were obtained with both sequences in ECG triggered, breath hold, and with a 256 x 128 matrix. Resulting temporal resolution was 55 ms for echo planar imaging, and 71 ms for k-space segmented fast gradient echo sequence, respectively. Ventricular volume and ejection fraction of both ventricles and left ventricular mass obtained with multi-shot echo planar imaging were assessed in comparison with k-space segmented fast gradient echo sequence. Measurements of left ventricular volume, ejection fraction and mass obtained with multi-shot echo planar imaging demonstrated close correlation with those obtained with k-space segmented fast gradient echo sequence. Right ventricular volumes obtained with echo planar imaging were significantly higher than those obtained with k-space segmented fast gradient echo sequence. This tendency is considered to be due to differing contrast between right ventricular myocardium and fat tissue observed with echo planar imaging relative to that observed with fast gradient echo sequence, because fat suppression is always performed in echo planar images. Multi-shot echo planar imaging can be a reliable tool for measurement of cardiac functional parameters, although wall motion analysis of the left ventricle requires higher temporal resolution and a short axial section. (K.H.)

Scanning transmission X-ray microscopy as a speciation tool for natural organic molecules

Energy Technology Data Exchange (ETDEWEB)

Rothe, J.; Plaschke, M.; Denecke, M.A. [Inst. fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, Karlsruhe (Germany)

2004-07-01

A molecular-scale understanding of the basic processes affecting stability and transport behavior of actinide cations, complexes or hydroxide ('eigencolloid') species is prerequisite to performance assessment of nuclear waste disposal in geological formations. Depending on their functional group chemistry and macromolecular structure, naturally occurring organic molecules (NOM) possess a high tendency towards actinide complexation reactions. However, the compositional and structural heterogeneity of NOM and mixed aggregates with inorganic phases makes speciation by spectromicroscopy techniques highly desirable. The applicability of Scanning Transmission X-ray Microscopy (STXM) as a speciation tool for the characterization of NOM is demonstrated for a multifunctional natural organic acid (chlorogenic acid), Eu(III)-loaded humic acid (HA) aggregates and Eu(III)-oxo/hydroxide/HA hetero-aggregates. It is shown that in situ probing of HA functional group chemistry down to a spatial resolution < 100 nm (i.e., less than femto-liter sampled volumes) is feasible, at the same time revealing morphological details on NOM aggregates and NOM/mineral associations. (orig.)

Thermodynamic characteristics of the adsorption of organic molecules on modified MCM-41 adsorbents

Science.gov (United States)

Gus'kov, V. Yu.; Sukhareva, D. A.; Salikhova, G. R.; Karpov, S. I.; Kudasheva, F. Kh.; Roessner, F.; Borodina, E. V.

2017-07-01

The adsorption of a number of organic molecules on samples of MCM-41 adsorbent modified with dichloromethylphenylsilane and subsequently treated with sulfuric acid (MDCS) and N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride (MNM) is studied. Specific retention volumes equal to the Henry constant are determined by means of inverse gas chromatography at infinite dilution. The thermodynamic characteristics of adsorption, the dispersive and specific components of the Helmholtz energy of adsorption, and the increment of the methyl group to the heat of adsorption are calculated. It is shown that the grafting of aminosilane and phenylsilane groups enhances the forces of dispersion and reduces specific interactions. A greater drop in polarity is observed for MDCS than for MNM, due to the stronger polarity of amoinosilane; the enthalpy factor makes the main contribution to the adsorption of organic compounds on the investigated adsorbents. It is found that the MNM sample is capable of the irreversible adsorption of alcohols.

High-Efficiency BODIPY-Based Organic Photovoltaics

KAUST Repository

Chen, John J.; Conron, Sarah M.; Erwin, Patrick; Dimitriou, Michael; McAlahney, Kyle; Thompson, Mark E.

2015-01-01

© 2014 American Chemical Society. A benzannulated boron dipyrromethene (BODIPY, bDIP) molecule exhibiting strong absorption at 640 nm was synthesized. The organic dye was used in an organic solar cell as the electron donor with C60 as the acceptor. The BODIPY dye demonstrated the best performance in lamellar architecture (indium tin oxide (ITO)/bDIP/C60/bathocuproine/Al), giving power conversion efficiency up to 4.5% with short-circuit current (JSC) of 8.7 mA/cm2 and an open-circuit voltage (VOC) of 0.81 V. Neutron reflectivity experiments were performed on the bilayer film to investigate the thickness dependence of JSC. A 13 nm mixed layer was found to be present at the donor/acceptor interface in the bilayer device, formed when the C60 was deposited onto a room temperature bDIP film. Planar-mixed heterojunction devices were fabricated to understand the extent of spontaneous mixing between the donor and acceptor materials. The native mixed region in the bilayer device was shown to most resemble 1:3 bDIP:C60 layer in the structure: (ITO/bDIP/bDIP:C60 blend/C60/bathocuproine/Al).

High-Efficiency BODIPY-Based Organic Photovoltaics

KAUST Repository

Chen, John J.

2015-01-14

© 2014 American Chemical Society. A benzannulated boron dipyrromethene (BODIPY, bDIP) molecule exhibiting strong absorption at 640 nm was synthesized. The organic dye was used in an organic solar cell as the electron donor with C60 as the acceptor. The BODIPY dye demonstrated the best performance in lamellar architecture (indium tin oxide (ITO)/bDIP/C60/bathocuproine/Al), giving power conversion efficiency up to 4.5% with short-circuit current (JSC) of 8.7 mA/cm2 and an open-circuit voltage (VOC) of 0.81 V. Neutron reflectivity experiments were performed on the bilayer film to investigate the thickness dependence of JSC. A 13 nm mixed layer was found to be present at the donor/acceptor interface in the bilayer device, formed when the C60 was deposited onto a room temperature bDIP film. Planar-mixed heterojunction devices were fabricated to understand the extent of spontaneous mixing between the donor and acceptor materials. The native mixed region in the bilayer device was shown to most resemble 1:3 bDIP:C60 layer in the structure: (ITO/bDIP/bDIP:C60 blend/C60/bathocuproine/Al).

Water and oxygen induced degradation of small molecule organic solar cells

DEFF Research Database (Denmark)

Hermenau, Martin; Riede, Moritz; Leo, Karl

2011-01-01

Small molecule organic solar cells were studied with respect to water and oxygen induced degradation by mapping the spatial distribution of reaction products in order to elucidate the degradation patterns and failure mechanisms. The active layers consist of a 30 nm bulk heterojunction formed......,4′-diamine p-doped with C60F36 (MeO-TPD:C60F36), which acted as hole transporting layer. Indium-tin-oxide (ITO) and aluminum served as hole and electron collecting electrode, respectively. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) in conjunction...... of aluminum oxide at the BPhen/Al interface, and diffusion of water into the ZnPc:C60 layer where ZnPc becomes oxidized. Finally, diffusion from the electrodes was found to have no or a negligible effect on the device lifetime....

Generators for finite depth subfactor planar algebras

Indian Academy of Sciences (India)

The main result of Kodiyalam and Tupurani [3] shows that a subfactor planar algebra of finite depth is singly generated with a finite presentation. If P is a subfactor planar algebra of depth k, it is shown there that a single 2k-box generates P. It is natural to ask what the smallest s is such that a single s-box generates P. While ...

Evanescent field refractometry in planar optical fiber.

Science.gov (United States)

Holmes, Christopher; Jantzen, Alexander; Gray, Alan C; Gow, Paul C; Carpenter, Lewis G; Bannerman, Rex H S; Gates, James C; Smith, Peter G R

2018-02-15

This Letter demonstrates a refractometer in integrated optical fiber, a new optical platform that planarizes fiber using flame hydrolysis deposition (FHD). The unique advantage of the technology is survivability in harsh environments. The platform is mechanically robust, and can survive elevated temperatures approaching 1000°C and exposure to common solvents, including acetone, gasoline, and methanol. For the demonstrated refractometer, fabrication was achieved through wet etching an SMF-28 fiber to a diameter of 8 μm before FHD planarization. An external refractive index was monitored using fiber Bragg gratings (FBGs), written into the core of the planarized fiber. A direct comparison to alternative FBG refractometers is made, for which the developed platform is shown to have comparable sensitivity, with the added advantage of survivability in harsh environments.

Observation and control of coherent torsional dynamics in a quinquethiophene molecule.

Science.gov (United States)

Cirmi, Giovanni; Brida, Daniele; Gambetta, Alessio; Piacenza, Manuel; Della Sala, Fabio; Favaretto, Laura; Cerullo, Giulio; Lanzani, Guglielmo

2010-07-28

By applying femtosecond pump-probe spectroscopy to a substituted quinquethiophene molecule in solution, we observe in the time domain the coherent torsional dynamics that drives planarization of the excited state. Our interpretation is based on numerical modeling of the ground and excited state potential energy surfaces and simulation of wavepacket dynamics, which reveals two symmetric excited state deactivation pathways per oscillation period. We use the acquired knowledge on torsional dynamics to coherently control the excited state population with a pump-dump scheme, exploiting the non-stationary Franck-Condon overlap between ground and excited states.

High efficiency organic photovoltaic cells employing hybridized mixed-planar heterojunctions

Science.gov (United States)

Xue, Jiangeng; Uchida, Soichi; Rand, Barry P; Forrest, Stephen

2013-11-19

A device is provided, having a first electrode, a second electrode, and a photoactive region disposed between the first electrode and the second electrode. The photoactive region includes a first organic layer comprising a mixture of an organic acceptor material and an organic donor material, wherein the first organic layer has a thickness not greater than 0.8 characteristic charge transport lengths, and a second organic layer in direct contact with the first organic layer, wherein: the second organic layer comprises an unmixed layer of the organic acceptor material or the organic donor material of the first organic layer, and the second organic layer has a thickness not less than about 0.1 optical absorption lengths. Preferably, the first organic layer has a thickness not greater than 0.3 characteristic charge transport lengths. Preferably, the second organic layer has a thickness of not less than about 0.2 optical absorption lengths. Embodiments of the invention can be capable of power efficiencies of 2% or greater, and preferably 5% or greater.

Nonlinear Saturation Amplitude in Classical Planar Richtmyer–Meshkov Instability

International Nuclear Information System (INIS)

Liu Wan-Hai; Jiang Hong-Bin; Ma Wen-Fang; Wang Xiang

2016-01-01

The classical planar Richtmyer–Meshkov instability (RMI) at a fluid interface supported by a constant pressure is investigated by a formal perturbation expansion up to the third order, and then according to definition of nonlinear saturation amplitude (NSA) in Rayleigh–Taylor instability (RTI), the NSA in planar RMI is obtained explicitly. It is found that the NSA in planar RMI is affected by the initial perturbation wavelength and the initial amplitude of the interface, while the effect of the initial amplitude of the interface on the NSA is less than that of the initial perturbation wavelength. Without marginal influence of the initial amplitude, the NSA increases linearly with wavelength. The NSA normalized by the wavelength in planar RMI is about 0.11, larger than that corresponding to RTI. (paper)

Nucleation and growth of copper phthalocyanine aggregates deposited from solution on planar surfaces

Energy Technology Data Exchange (ETDEWEB)

Ghani, Fatemeh [Department of Theory & Bio-Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1 Golm, 14476 Potsdam (Germany); Gojzewski, Hubert, E-mail: hubert.gojzewski@put.poznan.pl [Department of Theory & Bio-Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1 Golm, 14476 Potsdam (Germany); Institute of Physics, Poznan University of Technology, Piotrowo 3, 60-965 Poznan (Poland); Riegler, Hans [Department of Theory & Bio-Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1 Golm, 14476 Potsdam (Germany)

2015-10-01

Graphical abstract: - Highlights: • Copper phthalocyanine deposited on planar surfaces by 3 solution process methods. • Aggregate morphology examined for coverage extending over 3 orders of magnitude. • Morphologies vary from small individual domains to mesh-like multilayers. • Nucleation and growth model explains the observed deposit morphologies. - Abstract: Copper phthalocyanine (CuPc) dissolved in trifluoroacetic acid (TFA) is deposited on solid SiO{sub 2} surfaces by solvent evaporation. The deposited CuPc aggregates are investigated by atomic force microscopy (AFM). The CuPc deposits were prepared by spin casting, dip coating, and spray deposition. Depending on the amount of deposited CuPc the aggregate morphology ranges from small individual domains to mesh-like multilayers. Each domain/layer consists of many parallel stacks of CuPc molecules with the square, plate-like molecules piled face-wise within each stack. The parallel stacks are attached sideways (i.e., edgewise attachment molecularly) to the substrate forming “nanoribbons” with uniform thickness of about 1 nm and varying width. The thickness reflects the length of a molecular edge, the width the number of stacks. A nucleation and growth model is presented that explains the observed aggregate and multilayer morphologies as result of the combination of nucleation, transport processes and a consequence of the anisotropic intermolecular interactions due to the shape of the CuPc molecule.

The peeling process of infinite Boltzmann planar maps

DEFF Research Database (Denmark)

Budd, Timothy George

2016-01-01

criterion has a very simple interpretation. The finite random planar maps under consideration were recently proved to possess a well-defined local limit known as the infinite Boltzmann planar map (IBPM). Inspired by recent work of Curien and Le Gall, we show that the peeling process on the IBPM can...

Planar dynamical systems selected classical problems

CERN Document Server

Liu, Yirong; Huang, Wentao

2014-01-01

This book presents in an elementary way the recent significant developments in the qualitative theory of planar dynamical systems. The subjects are covered as follows: the studies of center and isochronous center problems, multiple Hopf bifurcations and local and global bifurcations of the equivariant planar vector fields which concern with Hilbert's 16th problem. This book is intended for graduate students, post-doctors and researchers in the area of theories and applications of dynamical systems. For all engineers who are interested the theory of dynamical systems, it is also a reasona

Electron Accumulative Molecules.

Science.gov (United States)

Buades, Ana B; Sanchez Arderiu, Víctor; Olid-Britos, David; Viñas, Clara; Sillanpää, Reijo; Haukka, Matti; Fontrodona, Xavier; Paradinas, Markos; Ocal, Carmen; Teixidor, Francesc

2018-02-28

With the goal to produce molecules with high electron accepting capacity and low reorganization energy upon gaining one or more electrons, a synthesis procedure leading to the formation of a B-N(aromatic) bond in a cluster has been developed. The research was focused on the development of a molecular structure able to accept and release a specific number of electrons without decomposing or change in its structural arrangement. The synthetic procedure consists of a parallel decomposition reaction to generate a reactive electrophile and a synthesis reaction to generate the B-N(aromatic) bond. This procedure has paved the way to produce the metallacarboranylviologen [M(C 2 B 9 H 11 )(C 2 B 9 H 10 )-NC 5 H 4 -C 5 H 4 N-M'(C 2 B 9 H 11 )(C 2 B 9 H 10 )] (M = M' = Co, Fe and M = Co and M' = Fe) and semi(metallacarboranyl)viologen [3,3'-M(8-(NC 5 H 4 -C 5 H 4 N-1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )] (M = Co, Fe) electron cumulative molecules. These molecules are able to accept up to five electrons and to donate one in single electron steps at accessible potentials and in a reversible way. By targeted synthesis and corresponding electrochemical tests each electron transfer (ET) step has been assigned to specific fragments of the molecules. The molecules have been carefully characterized, and the electronic communication between both metal centers (when this situation applies) has been definitely observed through the coplanarity of both pyridine fragments. The structural characteristics of these molecules imply a low reorganization energy that is a necessary requirement for low energy ET processes. This makes them electronically comparable to fullerenes, but on their side, they have a wide range of possible solvents. The ET from one molecule to another has been clearly demonstrated as well as their self-organizing capacity. We consider that these molecules, thanks to their easy synthesis, ET, self-organizing capacity, wide range of solubility, and easy processability, can

Solution-Processed Organic Solar Cells from Dye Molecules: An Investigation of Diketopyrrolopyrrole:Vinazene Heterojunctions

KAUST Repository

Walker, Bright

2012-01-25

Although one of the most attractive aspects of organic solar cells is their low cost and ease of fabrication, the active materials incorporated into the vast majority of reported bulk heterojunction (BHJ) solar cells include a semiconducting polymer and a fullerene derivative, classes of materials which are both typically difficult and expensive to prepare. In this study, we demonstrate that effective BHJs can be fabricated from two easily synthesized dye molecules. Solar cells incorporating a diketopyrrolopyrrole (DPP)-based molecule as a donor and a dicyanoimidazole (Vinazene) acceptor function as an active layer in BHJ solar cells, producing relatively high open circuit voltages and power conversion efficiencies (PCEs) up to 1.1%. Atomic force microscope images of the films show that active layers are rough and apparently have large donor and acceptor domains on the surface, whereas photoluminescence of the blends is incompletely quenched, suggesting that higher PCEs might be obtained if the morphology could be improved to yield smaller domain sizes and a larger interfacial area between donor and acceptor phases. © 2011 American Chemical Society.

Current in heavy-current planar diode with discrete emission surface

International Nuclear Information System (INIS)

Belomyttsev, S.Ya.; Korovin, S.D.; Pegel', I.V

1999-01-01

Dependence of current in a high-current planar diode on the size of emission centres was studied. Essential effect of emission surface microstructure on the current value in the planar diode was demonstrated. It was determined that if the distance between the emitter essentially exceeded their size then current dependence on the ratio of size to the value of the diode gap was an exponential function with 3/2 index. Current dependence on voltage obeyed the exponential law with 3/2 index up to higher voltage values in the planar diode with discrete emission surface in contrast to the case of a planar diode with homogeneous emission surface [ru

Single molecules and nanotechnology

CERN Document Server

Vogel, Horst

2007-01-01

This book focuses on recent advances in the rapidly evolving field of single molecule research. These advances are of importance for the investigation of biopolymers and cellular biochemical reactions, and are essential to the development of quantitative biology. Written by leading experts in the field, the articles cover a broad range of topics, including: quantum photonics of organic dyes and inorganic nanoparticles their use in detecting properties of single molecules the monitoring of single molecule (enzymatic) reactions single protein (un)folding in nanometer-sized confined volumes the dynamics of molecular interactions in biological cells The book is written for advanced students and scientists who wish to survey the concepts, techniques and results of single molecule research and assess them for their own scientific activities.

Controlling the Morphology of BDTT-DPP-Based Small Molecules via End-Group Functionalization for Highly Efficient Single and Tandem Organic Photovoltaic Cells.

Science.gov (United States)

Kim, Ji-Hoon; Park, Jong Baek; Yang, Hoichang; Jung, In Hwan; Yoon, Sung Cheol; Kim, Dongwook; Hwang, Do-Hoon

2015-11-04

A series of narrow-band gap, π-conjugated small molecules based on diketopyrrolopyrrole (DPP) electron acceptor units coupled with alkylthienyl-substituted-benzodithiophene (BDTT) electron donors were designed and synthesized for use as donor materials in solution-processed organic photovoltaic cells. In particular, by end-group functionalization of the small molecules with fluorine derivatives, the nanoscale morphologies of the photoactive layers of the photovoltaic cells were successfully controlled. The influences of different fluorine-based end-groups on the optoelectronic and morphological properties, carrier mobilities, and the photovoltaic performances of these materials were investigated. A high power conversion efficiency (PCE) of 6.00% under simulated solar light (AM 1.5G) illumination has been achieved for organic photovoltaic cells based on a small-molecule bulk heterojunction system consisting of a trifluoromethylbenzene (CF3) end-group-containing oligomer (BDTT-(DPP)2-CF3) as the donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor. As a result, the introduction of CF3 end-groups has been found to enhance both the short circuit current density (JSC) and fill factor (FF). A tandem photovoltaic device comprising an inverted BDTT-(DPP)2-CF3:PC71BM cell and a poly(3-hexylthiophene) (P3HT):indene-C60-bisadduct (IC60BA)-based cell as the top and bottom cell components, respectively, showed a maximum PCE of 8.30%. These results provide valuable guidelines for the rational design of conjugated small molecules for applications in high-performance organic photovoltaic cells. Furthermore, to the best of our knowledge, this is the first report on the design of fluorine-functionalized BDTT-DPP-based small molecules, which have been shown to be a viable candidate for use in inverted tandem cells.

Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

Science.gov (United States)

Tentscher, Peter R; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J; Arey, J Samuel

2015-01-08

To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

Stability of metal organic frameworks and interaction of small gas molecules in these materials

Science.gov (United States)

Tan, Kui

The work in this dissertation combines spectroscopy ( in-situ infrared absorption and Raman), powder X-ray diffraction and DFT calculations to study the stability of metal organic frameworks materials (MOFs) in the presence of water vapor and other corrosive gases (e.g., SO 2, NO2 NO), and the interaction and competitive co-adsorption of several gases within MOFs by considering two types of prototypical MOFs: 1) a MOF with saturated metal centers based on paddlewheel secondary building units: M(bdc)(ted)0.5 [M=Cu, Zn, Ni, Co, bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine], and 2) a MOF with unsaturated metal centers: M2(dobdc) [M=Mg2+, Zn2+, Ni2+, Co2+ and dobdc = 2,5-dihydroxybenzenedicarboxylate]. We find that the stability of MOFs to water vapor critically depends on their structure and the specific metal cation in the building units. For M(bdc)(ted)0.5, the metal-bdc bond is the most vulnerable for Cu(bdc)(ted)0.5, while the metal-ted bond is first attacked for the Zn and Co analogs. In contrast, Ni(bdc)(ted)0.5 remains stable under the same conditions. For M2(dobdc), or MOF-74, the weak link is the dobdc-metal bond. The water molecule is dissociatively adsorbed at the metal-oxygen group with OH adsorption directly on the metal center and H adsorption on the bridging O of the phenolate group in the dobdc linker. Other technologically important molecules besides water, such as NO, NO2, SO2, tend to poison M2(dobdc) through dissociative or molecular adsorption onto the open metal sites. A high uptake SO2 capacity was measured in M(bdc)(ted)0.5, attributed to multipoint interactions between the guest SO2 molecule and the MOF host. In the case of competitive co-adsorption between CO2 and other small molecules, we find that binding energy alone is not a good indicator of molecular site occupation within the MOF (i.e., it cannot successfully predict and evaluate the displacement of CO2 by other molecules). Instead, we show that the kinetic barrier for the

Planar Submillimeter-Wave Mixer Technology with Integrated Antenna

Science.gov (United States)

Chattopadhyay, Gautam; Mehdi, Imran; Gill, John J.; Lee, Choonsup; lombart, Muria L.; Thomas, Betrand

2010-01-01

High-performance mixers at terahertz frequencies require good matching between the coupling circuits such as antennas and local oscillators and the diode embedding impedance. With the availability of amplifiers at submillimeter wavelengths and the need to have multi-pixel imagers and cameras, planar mixer architecture is required to have an integrated system. An integrated mixer with planar antenna provides a compact and optimized design at terahertz frequencies. Moreover, it leads to a planar architecture that enables efficient interconnect with submillimeter-wave amplifiers. In this architecture, a planar slot antenna is designed on a thin gallium arsenide (GaAs) membrane in such a way that the beam on either side of the membrane is symmetric and has good beam profile with high coupling efficiency. A coplanar waveguide (CPW) coupled Schottky diode mixer is designed and integrated with the antenna. In this architecture, the local oscillator (LO) is coupled through one side of the antenna and the RF from the other side, without requiring any beam sp litters or diplexers. The intermediate frequency (IF) comes out on a 50-ohm CPW line at the edge of the mixer chip, which can be wire-bonded to external circuits. This unique terahertz mixer has an integrated single planar antenna for coupling both the radio frequency (RF) input and LO injection without any diplexer or beamsplitters. The design utilizes novel planar slot antenna architecture on a 3- mthick GaAs membrane. This work is required to enable future multi-pixel terahertz receivers for astrophysics missions, and lightweight and compact receivers for planetary missions to the outer planets in our solar system. Also, this technology can be used in tera hertz radar imaging applications as well as for testing of quantum cascade lasers (QCLs).

Linear Ion Traps in Space: The Mars Organic Molecule Analyzer (MOMA) Instrument and Beyond

Science.gov (United States)

Arevalo, Ricardo; Brinckerhoff, William; Mahaffy, Paul; van Amerom, Friso; Danell, Ryan; Pinnick, Veronica; Li, Xiang; Hovmand, Lars; Getty, Stephanie; Grubisic, Andrej; Goesmann, Fred; Cottin, Hervé

2015-11-01

Historically, quadrupole mass spectrometer (QMS) instruments have been used to explore a wide survey of planetary targets in our solar system, from Venus (Pioneer Venus) to Saturn (Cassini-Huygens). However, linear ion trap (LIT) mass spectrometers have found a niche as smaller, versatile alternatives to traditional quadrupole analyzers.The core astrobiological experiment of ESA’s ExoMars Program is the Mars Organic Molecule Analyzer (MOMA) onboard the ExoMars 2018 rover. The MOMA instrument is centered on a linear (or 2-D) ion trap mass spectrometer. As opposed to 3-D traps, LIT-based instruments accommodate two symmetrical ion injection pathways, enabling two complementary ion sources to be used. In the case of MOMA, these two analytical approaches are laser desorption mass spectrometry (LDMS) at Mars ambient pressures, and traditional gas chromatography mass spectrometry (GCMS). The LIT analyzer employed by MOMA also offers: higher ion capacity compared to a 3-D trap of the same volume; redundant detection subassemblies for extended lifetime; and, a link to heritage QMS designs and assembly logistics. The MOMA engineering test unit (ETU) has demonstrated the detection of organics in the presence of wt.%-levels of perchlorate, effective ion enhancement via stored waveform inverse Fourier transform (SWIFT), and derivation of structural information through tandem mass spectrometry (MS/MS).A more progressive linear ion trap mass spectrometer (LITMS), funded by the NASA ROSES MatISSE Program, is being developed at NASA GSFC and promises to augment the capabilities of the MOMA instrument by way of: an expanded mass range (i.e., 20 - 2000 Da); detection of both positive and negative ions; spatially resolved (<1 mm) characterization of individual rock core layers; and, evolved gas analysis and GCMS with pyrolysis up to 1300° C (enabling breakdown of refractory phases). The Advanced Resolution Organic Molecule Analyzer (AROMA) instrument, being developed through NASA

High mobility high efficiency organic films based on pure organic materials

Science.gov (United States)

Salzman, Rhonda F [Ann Arbor, MI; Forrest, Stephen R [Ann Arbor, MI

2009-01-27

A method of purifying small molecule organic material, performed as a series of operations beginning with a first sample of the organic small molecule material. The first step is to purify the organic small molecule material by thermal gradient sublimation. The second step is to test the purity of at least one sample from the purified organic small molecule material by spectroscopy. The third step is to repeat the first through third steps on the purified small molecule material if the spectroscopic testing reveals any peaks exceeding a threshold percentage of a magnitude of a characteristic peak of a target organic small molecule. The steps are performed at least twice. The threshold percentage is at most 10%. Preferably the threshold percentage is 5% and more preferably 2%. The threshold percentage may be selected based on the spectra of past samples that achieved target performance characteristics in finished devices.

Hydrogenated arsenenes as planar magnet and Dirac material

Energy Technology Data Exchange (ETDEWEB)

Zhang, Shengli; Cai, Bo; Zeng, Haibo, E-mail: Huziyu@csrc.ac.cn, E-mail: zeng.haibo@njust.edu.cn [Institute of Optoelectronics and Nanomaterials, Herbert Gleiter Institute of Nanoscience, College of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); Hu, Yonghong [Institute of Optoelectronics and Nanomaterials, Herbert Gleiter Institute of Nanoscience, College of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing 210094 (China); School of Nuclear Technology and Chemistry and Biology, Hubei University of Science and Technology, Xianning 437100 (China); Hu, Ziyu, E-mail: Huziyu@csrc.ac.cn, E-mail: zeng.haibo@njust.edu.cn [Beijing Computational Science Research Center, Beijing 100084 (China)

2015-07-13

Arsenene and antimonene are predicted to have 2.49 and 2.28 eV band gaps, which have aroused intense interest in the two-dimensional (2D) semiconductors for nanoelectronic and optoelectronic devices. Here, the hydrogenated arsenenes are reported to be planar magnet and 2D Dirac materials based on comprehensive first-principles calculations. The semi-hydrogenated (SH) arsenene is found to be a quasi-planar magnet, while the fully hydrogenated (FH) arsenene is a planar Dirac material. The buckling height of pristine arsenene is greatly decreased by the hydrogenation, resulting in a planar and relatively low-mass-density sheet. The electronic structures of arsenene are also evidently altered after hydrogenating from wide-band-gap semiconductor to metallic material for SH arsenene, and then to Dirac material for FH arsenene. The SH arsenene has an obvious magnetism, mainly contributed by the p orbital of the unsaturated As atom. Such magnetic and Dirac materials modified by hydrogenation of arsenene may have potential applications in future optoelectronic and spintronic devices.

Hydrogenated arsenenes as planar magnet and Dirac material

International Nuclear Information System (INIS)

Zhang, Shengli; Cai, Bo; Zeng, Haibo; Hu, Yonghong; Hu, Ziyu

2015-01-01

Arsenene and antimonene are predicted to have 2.49 and 2.28 eV band gaps, which have aroused intense interest in the two-dimensional (2D) semiconductors for nanoelectronic and optoelectronic devices. Here, the hydrogenated arsenenes are reported to be planar magnet and 2D Dirac materials based on comprehensive first-principles calculations. The semi-hydrogenated (SH) arsenene is found to be a quasi-planar magnet, while the fully hydrogenated (FH) arsenene is a planar Dirac material. The buckling height of pristine arsenene is greatly decreased by the hydrogenation, resulting in a planar and relatively low-mass-density sheet. The electronic structures of arsenene are also evidently altered after hydrogenating from wide-band-gap semiconductor to metallic material for SH arsenene, and then to Dirac material for FH arsenene. The SH arsenene has an obvious magnetism, mainly contributed by the p orbital of the unsaturated As atom. Such magnetic and Dirac materials modified by hydrogenation of arsenene may have potential applications in future optoelectronic and spintronic devices

Hydrogenated arsenenes as planar magnet and Dirac material

Science.gov (United States)

Zhang, Shengli; Hu, Yonghong; Hu, Ziyu; Cai, Bo; Zeng, Haibo

2015-07-01

Arsenene and antimonene are predicted to have 2.49 and 2.28 eV band gaps, which have aroused intense interest in the two-dimensional (2D) semiconductors for nanoelectronic and optoelectronic devices. Here, the hydrogenated arsenenes are reported to be planar magnet and 2D Dirac materials based on comprehensive first-principles calculations. The semi-hydrogenated (SH) arsenene is found to be a quasi-planar magnet, while the fully hydrogenated (FH) arsenene is a planar Dirac material. The buckling height of pristine arsenene is greatly decreased by the hydrogenation, resulting in a planar and relatively low-mass-density sheet. The electronic structures of arsenene are also evidently altered after hydrogenating from wide-band-gap semiconductor to metallic material for SH arsenene, and then to Dirac material for FH arsenene. The SH arsenene has an obvious magnetism, mainly contributed by the p orbital of the unsaturated As atom. Such magnetic and Dirac materials modified by hydrogenation of arsenene may have potential applications in future optoelectronic and spintronic devices.

Algorithm for advanced canonical coding of planar chemical structures that considers stereochemical and symmetric information.

Science.gov (United States)

Koichi, Shungo; Iwata, Satoru; Uno, Takeaki; Koshino, Hiroyuki; Satoh, Hiroko

2007-01-01

We describe a rigorous and fast algorithm for advanced canonical coding of planar chemical structures based on the algorithm of Faulon et al. (J. Chem. Inf. Comput. Sci. 2004, 44, 427-436). Our algorithm works well even for highly symmetric structures; moreover, an advantage of our algorithm includes providing a rigorous canonical numbering of atoms with a consideration of stereochemistry and recognizing symmetric moieties. The planar structural line notation with the canonical numbering is also fit for use with stereochemical line notation. These capabilities are usable for general purposes in chemical structural coding and are particularly essential for detecting equivalent atoms in NMR studies. This algorithm was implemented on a 13C NMR chemical shift prediction system CAST/CNMR. Applications of the algorithm to several organic compounds demonstrate the practical efficiency of the rigorous coding.

The number of colorings of planar graphs with no separating triangles

DEFF Research Database (Denmark)

Thomassen, Carsten

2017-01-01

A classical result of Birkhoff and Lewis implies that every planar graph with . n vertices has at least . 152n-1 distinct 5-vertex-colorings. Equality holds for planar triangulations with . n-4 separating triangles. We show that, if a planar graph has no separating triangle, then it has at least ...

Planar geometry of 4-substituted-2,2'-bipyridines synthesized by Sonogashira and Suzuki cross-coupling reactions

Energy Technology Data Exchange (ETDEWEB)

Luong Thi, T. T., E-mail: thuyltt@hnue.edu.vn; Nguyen Bich, N.; Nguyen, H. [Hanoi National University of Education, Chemistry Department (Viet Nam); Van Meervelt, L., E-mail: luc.vanmeervelt@chem.kuleuven.be [KU Leuven, Chemistry Department (Belgium)

2015-12-15

Two 4-substituted 2,2'-bipyridines, namely 4-(ferrocenylethynyl)-2,2'-bipyridine (I) and 4-ferrocenyl-2,2'-bipyridine (II) have been synthesized and fully characterized via single-crystal X-ray diffraction and {sup 1}H and {sup 13}C NMR analyses. The π-conjugated system designed from 2,2'-bipyridine modified with the ferrocenylethynyl and ferrocenyl groups shows the desired planarity. In the crystal packing of I and II, the molecules arrange themselves in head-to-tail and head-to-head motifs, respectively, resulting in consecutive layers of ferrocene and pyridine moieties.

Determination of crystallographic and macroscopic orientation of planar structures in TEM

DEFF Research Database (Denmark)

Huang, X.; Liu, Q.

1998-01-01

With the aid of a double-tilt holder in a transmission electron microscope (TEM), simple methods are described for determination of the crystallographic orientation of a planar structure and for calculation of the macroscopic orientation of the planar structure. The correlation between a planar...... structure and a crystallographic plane can be found by comparing the differences in their trace directions on the projection plane and inclination angles with respect to that plane. The angles between the traces of planar structures and the sample axis measured from the TEM micrographs, which have been...

CAL3JHH: a Java program to calculate the vicinal coupling constants (3J H,H) of organic molecules.

Science.gov (United States)

Aguirre-Valderrama, Alonso; Dobado, José A

2008-12-01

Here, we present a free web-accessible application, developed in the JAVA programming language for the calculation of vicinal coupling constant (3J(H,H)) of organic molecules with the H-Csp3-Csp3-H fragment. This JAVA applet is oriented to assist chemists in structural and conformational analyses, allowing the user to calculate the averaged 3J(H,H) values among conformers, according to its Boltzmann populations. Thus, the CAL3JHH program uses the Haasnoot-Leeuw-Altona equation, and, by reading the molecule geometry from a protein data bank (PDB) file format or from multiple pdb files, automatically detects all the coupled hydrogens, evaluating the data needed for this equation. Moreover, a "Graphical viewer" menu allows the display of the results on the 3D molecule structure, as well as the plotting of the Newman projection for the couplings.

High-Performance CH3NH3PbI3-Inverted Planar Perovskite Solar Cells with Fill Factor Over 83% via Excess Organic/Inorganic Halide.

Science.gov (United States)

Jahandar, Muhammad; Khan, Nasir; Lee, Hang Ken; Lee, Sang Kyu; Shin, Won Suk; Lee, Jong-Cheol; Song, Chang Eun; Moon, Sang-Jin

2017-10-18

The reduction of charge carrier recombination and intrinsic defect density in organic-inorganic halide perovskite absorber materials is a prerequisite to achieving high-performance perovskite solar cells with good efficiency and stability. Here, we fabricated inverted planar perovskite solar cells by incorporation of a small amount of excess organic/inorganic halide (methylammonium iodide (CH 3 NH 3 I; MAI), formamidinium iodide (CH(NH 2 ) 2 I; FAI), and cesium iodide (CsI)) in CH 3 NH 3 PbI 3 perovskite film. Larger crystalline grains and enhanced crystallinity in CH 3 NH 3 PbI 3 perovskite films with excess organic/inorganic halide reduce the charge carrier recombination and defect density, leading to enhanced device efficiency (MAI+: 14.49 ± 0.30%, FAI+: 16.22 ± 0.38% and CsI+: 17.52 ± 0.56%) compared to the efficiency of a control MAPbI 3 device (MAI: 12.63 ± 0.64%) and device stability. Especially, the incorporation of a small amount of excess CsI in MAPbI 3 perovskite film leads to a highly reproducible fill factor of over 83%, increased open-circuit voltage (from 0.946 to 1.042 V), and short-circuit current density (from 18.43 to 20.89 mA/cm 2 ).

Focused Role of an Organic Small-Molecule PBD on Performance of the Bistable Resistive Switching.

Science.gov (United States)

Li, Lei; Sun, Yanmei; Ai, Chunpeng; Lu, Junguo; Wen, Dianzhong; Bai, Xuduo

2015-12-01

An undoped organic small-molecule 2-(4-tert-butylphenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole (PBD) and a kind of nanocomposite blending poly(methyl methacrylate) (PMMA) into PBD are employed to implement bistable resistive switching. For the bistable resistive switching indium tin oxide (ITO)/PBD/Al, its ON/OFF current ratio can touch 6. What is more, the ON/OFF current ratio, approaching to 10(4), is available due to the storage layer PBD:PMMA with the chemical composition 1:1 in the bistable resistive switching ITO/PBD:PMMA/Al. The capacity, data retention of more than 1 year and endurance performance (>10(4) cycles) of ITO/PBD:PMMA(1:1)/Al, exhibits better stability and reliability of the samples, which underpins the technique and application of organic nonvolatile memory.

Manufacturing of planar ceramic interconnects

Energy Technology Data Exchange (ETDEWEB)

Armstrong, B.L.; Coffey, G.W.; Meinhardt, K.D.; Armstrong, T.R. [Pacific Northwest National Lab., Richland, WA (United States)

1996-12-31

The fabrication of ceramic interconnects for solid oxide fuel cells (SOFC) and separator plates for electrochemical separation devices has been a perennial challenge facing developers. Electrochemical vapor deposition (EVD), plasma spraying, pressing, tape casting and tape calendering are processes that are typically utilized to fabricate separator plates or interconnects for the various SOFC designs and electrochemical separation devices. For sake of brevity and the selection of a planar fuel cell or gas separation device design, pressing will be the only fabrication technique discussed here. This paper reports on the effect of the characteristics of two doped lanthanum manganite powders used in the initial studies as a planar porous separator for a fuel cell cathode and as a dense interconnect for an oxygen generator.

From Molecules to Living Organisms : an Interplay between Biology and Physics : Lecture Notes of the Les Houches School of Physics

CERN Document Server

Nury, Hughes; Parcy, François; Ruigrok, Rob W H; Ziegler, Christine; Cugliandolo, Leticia F; Session CII

2016-01-01

The aim of this book is to provide new ideas for studying living matter by a simultaneous understanding of behavior from molecules to the cell, to the whole organism in the light of physical concepts. Indeed, forces guide most biological phenomena. In some cases these forces can be well-described and thus used to model a particular biological phenomenon. This is exemplified here by the study of membranes, where their shapes and curvatures can be modeled using a limited number of parameters that are measured experimentally. The growth of plants is another example where the combination of physics, biology and mathematics leads to a predictive model. The laws of thermodynamics are essential, as they dictate the behavior of proteins, or more generally biological molecules, in an aqueous environment. Integrated studies from the molecule to a larger scale need a combination of cutting-edge approaches, such as the use of new X-ray sources, in-cell NMR, cryo-electron microscopy or single-molecule microscopy. Some are...

Excimers of organic molecules

Science.gov (United States)

Barashkov, Nikolai N.; Sakhno, T. V.; Nurmukhametov, Ravil'N.; Khakhel', O. A.

1993-06-01

Studies devoted to excimers in organic systems are surveyed. Processes leading to the excitation of the excimer luminescence are examined. Examples of the excimer-like glow of dimers are described. The relation between the structure of the complexes and their fluorescence properties is demonstrated. The bibliography includes 218 references.

High mass-resolution electron-ion-ion coincidence measurements on core-excited organic molecules

CERN Document Server

Tokushima, T; Senba, Y; Yoshida, H; Hiraya, A

2001-01-01

Total electron-ion-ion coincidence measurements on core excited organic molecules have been carried out with high mass resolution by using multimode (reflectron/linear) time-of-flight mass analyzer. From the ion correlation spectra of core excited CH sub 3 OH and CD sub 3 OH, the reaction pathway to form H sub 3 sup + (D sub 3 sup +) is identified as the elimination of three H (D) atoms from the methyl group, not as the inter-group (-CH sub 3 and -OH) interactions. In a PEPIPICO spectrum of acetylacetone (CH sub 3 COCH sub 2 COCH sub 3) measured by using a reflectron TOF, correlations between ions up to mass number 70 with one-mass resolution was recorded.

Mössbauer spectroscopic and powder X-ray diffraction studies on incorporation of gaseous organic molecules into intermolecular nano-voids of mixed-valence trinuclear iron pentafluorobenzoate complex

International Nuclear Information System (INIS)

Sakai, Yoichi; Onaka, Satoru; Ogiso, Ryo; Takayama, Tsutomu; Takahashi, Masashi; Nakamoto, Tadahiro

2013-01-01

Incorporation of gaseous organic molecules into polycrystalline mixed-valence trinuclear iron (Fe 3+ ,Fe 3+ ,Fe 2+ ) pentafluorobenzoate complex Fe 3 O(C 6 F 5 COO) 6 (C 5 H 5 N) 3 with intermolecular nano-voids was studied by 57 Fe-Mössbauer spectroscopic and powder XRD measurements. Organic-molecule incorporation was mainly chased by using iron-valence fluctuation observed in a Mössbauer spectrum, and also researched supportively by a powder XRD technique. (author)

The simple method to co-register planar image with photograph

International Nuclear Information System (INIS)

Jang, Sung June; Kim, Seok Ki; Kang, Keon Wook

2005-01-01

Generally scintigraphic image presents the highly specific functional information. Sometimes, there can be limited information of patients anatomical landmark required to identify the lesion in planar nuclear medicine image. In this study, we applied the simple fusion method of planar scintigraphy and plain photography and validated the techniques with our own software. We used three fiducial marks which were comprised with Tc-99m. We obtained planar image with single head gamma camera (ARGUS ADAC laboratory, USA) and photograph using a general digital camera (CANON JAPAN). The coordinates of three marks were obtained in photograph and planar scintigraphy image. Based on these points, we took affine transformation and then fused these two images. To evaluate the precision, we compared with different depth. To find out the depth of lesion, the images were acquired in different angles and we compared the real depth and the geometrically calculated depth. At the same depth with mark, the each discordance was less than 1 mm. When the photograph were taken at the distance with 1 m and 2 m, the point 30 cm off the center were discordant in 5 mm and 2 mm each. We used this method in the localization of the remnant thyroid tissue on I-131 whole body scan with photo image. The simple method to co-register planar image with photography was reliable and easy to use. By this method, we could localize the lesion on the planar scintigraphy more accurately with other planar images (i.e. photograph) and predict the depth of the lesion without tomographic image

Anisotrophic currents and flux jumps in high-T-c superconducting films with self-organized arrays of planar defects

DEFF Research Database (Denmark)

Yurchenko, V.V.; Qviller, A.J.; Mozhaev, P.B.

2010-01-01

Regular arrays of planar defects with a period of a few nanometers can be introduced in superconducting YBa2Cu3O7-delta (YBCO) thin films by depositing them on vicinal (also called miscut or tilted) substrates. This results in the anisotropy of critical currents flowing in the plane of the film. ...

Multiple atomic scale solid surface interconnects for atom circuits and molecule logic gates

International Nuclear Information System (INIS)

Joachim, C; Martrou, D; Gauthier, S; Rezeq, M; Troadec, C; Jie Deng; Chandrasekhar, N

2010-01-01

The scientific and technical challenges involved in building the planar electrical connection of an atomic scale circuit to N electrodes (N > 2) are discussed. The practical, laboratory scale approach explored today to assemble a multi-access atomic scale precision interconnection machine is presented. Depending on the surface electronic properties of the targeted substrates, two types of machines are considered: on moderate surface band gap materials, scanning tunneling microscopy can be combined with scanning electron microscopy to provide an efficient navigation system, while on wide surface band gap materials, atomic force microscopy can be used in conjunction with optical microscopy. The size of the planar part of the circuit should be minimized on moderate band gap surfaces to avoid current leakage, while this requirement does not apply to wide band gap surfaces. These constraints impose different methods of connection, which are thoroughly discussed, in particular regarding the recent progress in single atom and molecule manipulations on a surface.

Optical probing of single fluorescent molecules and proteins

NARCIS (Netherlands)

Garcia Parajo, M.F.; Veerman, J.A.; Bouwhuis, R.; Bouwhuis, Rudo; van Hulst, N.F.; Vallée, R.A.L.

2001-01-01

Single-molecule detection and analysis of organic fluorescent molecules and proteins are presented, with emphasis o­n the underlying principles methodology and the application of single-molecule analysis at room temperature. This Minireview is mainly focused o­n the application of confocal and

A study of coFeB magnetic yoke based on planar electromagnet

Science.gov (United States)

Qin, L.; Li, Q.; Yuan, Yong J.

2017-07-01

This paper studies the fabrication of a novel planar electromagnet consisting of a planar copper coil and a magnetic yoke. CoFeB was used as the magnetic yoke material instead of the traditional permanent magnets. The planar electromagnet was fabricated and optimized to maximize the electromagnetic force, especially with varying CoFeB thickness. The micro-planar electromagnet was fabricated successfully by the traditional micro-electro-mechanical-system (MEMS) techniques and XRD, VSM were used to characterize the performance of the electromagnet. The planar electromagnet exhibits superior perpendicular magnetic anisotropy (PMA) and 0.006 emu of MS was achieved following 2 min deposition of CoFeB thin film. By integrating with other micro apparatuses, it is anticipated that the planar electromagnet will have potential applications in areas such as biosensors, biological medicine, drug delivery, chemical analysis and environmental monitoring.

Raman studies of BEDT-TTF molecule-based organic superconductors

International Nuclear Information System (INIS)

Lin, Y.; Eldridge, J. E.; Schlueter, J.; Wang, H. H.; Kini, A. M.

2001-01-01

The temperature dependence of the frequencies of the Raman features due to ν 9 (A g ) and ν 60 (B 3g ) modes has been measured in the BEDT-TTF (ET) molecule-based organic superconductors κ-(ET) 2 Cu[N(CN) 2 ]Br, κ-(ET) 2 Cu[N(CN) 2 ]Cl, α t -(ET) 2 I 3 , and β-(ET) 2 AuI 2 . The frequency of the ν 9 (A g ) mode was observed to soften in κ-(ET) 2 Cu[N(CN) 2 ]Br and κ-(ET) 2 Cu[N(CN) 2 ]Cl at low temperatures where NMR data indicated antiferromagnetic fluctuations, providing evidence of spin-phonon interactions. The result is also compared with a very recent theory which deals with the effect of electronic correlations on the frequencies of the molecular phonon modes. We observed a peak splitting for the ν 60 (B 3g ) mode in α t -(ET) 2 I 3 below 190 K, where an incommensurate superstructure was reported, and a frequency decrease of 1.7±0.4 cm -1 for the upper component of the ν 60 (B 3g ) mode in the superconducting compound, demonstrating further the unusual properties of this mode

The Minimum Binding Energy and Size of Doubly Muonic D3 Molecule

Science.gov (United States)

Eskandari, M. R.; Faghihi, F.; Mahdavi, M.

The minimum energy and size of doubly muonic D3 molecule, which two of the electrons are replaced by the much heavier muons, are calculated by the well-known variational method. The calculations show that the system possesses two minimum positions, one at typically muonic distance and the second at the atomic distance. It is shown that at the muonic distance, the effective charge, zeff is 2.9. We assumed a symmetric planar vibrational model between two minima and an oscillation potential energy is approximated in this region.

Design and measurements of the double layer planar motor

NARCIS (Netherlands)

Rovers, J.M.M.; Jansen, J.W.; Lomonova, E.

2013-01-01

Moving-magnet magnetically levitated planar motors are considered for use as a wafer stage in the semiconductor lithographic industry. This puts high requirements on the accuracy and the dissipated power and cooling performance of such motors. A novel planar motor topology is developed, which

Quantitative determination of the organ distribution of the cell adhesion molecule cell-CAM 105 by radioimmunoassay

International Nuclear Information System (INIS)

Odin, P.; Oebrink, B.

1987-01-01

The authors have previously identified a 105,000-Da plasma membrane glycoprotein, denoted cell-CAM 105, that is involved in intercellular adhesion of reaggregating rat hepatocytes. In this communication they report on the development of a radioimmunoassay for cell-CAM 105, employing purified cell-CAM 105, specific antisera against the molecule, and formalin-fixed protein A-containing staphylococci for precipitation of the immune complexes. The assay was shown to be sensitive, specific, precise, rapid, and easy to perform. They used this radioimmunoassay in investigations of the occurrence of cell-CAM 105 in different rat organs. Cell-CAM 105 was present in a wide spectrum of organs in varying amounts. The highest concentrations were found in the gastrointestinal tract, liver, some secretory glands, vagina, kidney, and lung. The results were confirmed by immunoblotting, which revealed one distinct protein component, corresponding to cell-CAM 105, in each positive organ

Sample Analysis at Mars (SAM) and Mars Organic Molecule Analyzer (MOMA) as Critical In Situ Investigation for Targeting Mars Returned Samples

Science.gov (United States)

Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Szopa, C.; Buch, A.; Goesmann, F.; Goetz, W.; Raulin, F.; SAM Science Team; MOMA Science Team

2018-04-01

SAM (Curiosity) and MOMA (ExoMars) Mars instruments, seeking for organics and biosignatures, are essential to establish taphonomic windows of preservation of molecules, in order to target the most interesting samples to return from Mars.

A Dual Source Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer of ExoMars 2018

Science.gov (United States)

Brickerhoff, William B.; vanAmerom, F. H. W.; Danell, R. M.; Arevalo, R.; Atanassova, M.; Hovmand, L.; Mahaffy, P. R.; Cotter, R. J.

2011-01-01

We present details on the objectives, requirements, design and operational approach of the core mass spectrometer of the Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars mission. The MOMA mass spectrometer enables the investigation to fulfill its objective of analyzing the chemical composition of organic compounds in solid samples obtained from the near surface of Mars. Two methods of ionization are realized, associated with different modes of MOMA operation, in a single compact ion trap mass spectrometer. The stringent mass and power constraints of the mission have led to features such as low voltage and low frequency RF operation [1] and pulse counting detection.

Effect of nontronite smectite clay on the chemical evolution of several organic molecules under simulated martian surface ultraviolet radiation conditions.

Science.gov (United States)

Poch, Olivier; Jaber, Maguy; Stalport, Fabien; Nowak, Sophie; Georgelin, Thomas; Lambert, Jean-François; Szopa, Cyril; Coll, Patrice

2015-03-01

Most of the phyllosilicates detected at the surface of Mars today are probably remnants of ancient environments that sustained long-term bodies of liquid water at the surface or subsurface and were possibly favorable for the emergence of life. Consequently, phyllosilicates have become the main mineral target in the search for organics on Mars. But are phyllosilicates efficient at preserving organic molecules under current environmental conditions at the surface of Mars? We monitored the qualitative and quantitative evolutions of glycine, urea, and adenine in interaction with the Fe(3+)-smectite clay nontronite, one of the most abundant phyllosilicates present at the surface of Mars, under simulated martian surface ultraviolet light (190-400 nm), mean temperature (218 ± 2 K), and pressure (6 ± 1 mbar) in a laboratory simulation setup. We tested organic-rich samples that were representative of the evaporation of a small, warm pond of liquid water containing a high concentration of organics. For each molecule, we observed how the nontronite influences its quantum efficiency of photodecomposition and the nature of its solid evolution products. The results reveal a pronounced photoprotective effect of nontronite on the evolution of glycine and adenine; their efficiencies of photodecomposition were reduced by a factor of 5 when mixed at a concentration of 2.6 × 10(-2) mol of molecules per gram of nontronite. Moreover, when the amount of nontronite in the sample of glycine was increased by a factor of 2, the gain of photoprotection was multiplied by a factor of 5. This indicates that the photoprotection provided by the nontronite is not a purely mechanical shielding effect but is also due to stabilizing interactions. No new evolution product was firmly identified, but the results obtained with urea suggest a particular reactivity in the presence of nontronite, leading to an increase of its dissociation rate.

Dual Function Additives: A Small Molecule Crosslinker for Enhanced Efficiency and Stability in Organic Solar Cells

KAUST Repository

Rumer, Joseph W.; Ashraf, Raja S.; Eisenmenger, Nancy D.; Huang, Zhenggang; Meager, Iain; Nielsen, Christian B.; Schroeder, Bob C.; Chabinyc, Michael L.; McCulloch, Iain

2015-01-01

A bis-azide-based small molecule crosslinker is synthesized and evaluated as both a stabilizing and efficiency-boosting additive in bulk heterojunction organic photovoltaic cells. Activated by a noninvasive and scalable solution processing technique, polymer:fullerene blends exhibit improved thermal stability with suppressed polymer skin formation at the cathode and frustrated fullerene aggregation on ageing, with initial efficiency increased from 6% to 7%. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual Function Additives: A Small Molecule Crosslinker for Enhanced Efficiency and Stability in Organic Solar Cells

KAUST Repository

Rumer, Joseph W.

2015-02-01

A bis-azide-based small molecule crosslinker is synthesized and evaluated as both a stabilizing and efficiency-boosting additive in bulk heterojunction organic photovoltaic cells. Activated by a noninvasive and scalable solution processing technique, polymer:fullerene blends exhibit improved thermal stability with suppressed polymer skin formation at the cathode and frustrated fullerene aggregation on ageing, with initial efficiency increased from 6% to 7%. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative Study of Ether Group Molecules in Insoluble Organic Matter from Carbonaceous Chondrites by CuO-NaOH Selective Degradation

Science.gov (United States)

Yabuta, H.; Cody, G. D.; Alexander, C. M. O'd.

2006-03-01

CuO-NaOH degradation of the insoluble organic matter (IOM) from the Murchison meteorite was conducted. A variety of carboxylic acids were indentified. Oxalic acid was most abundant. It was estimated that approximately ~30% of the IOM included ether groups containing molecules.

Adaptive self-assembly and induced-fit transformations of anion-binding metal-organic macrocycles

Science.gov (United States)

Zhang, Ting; Zhou, Li-Peng; Guo, Xiao-Qing; Cai, Li-Xuan; Sun, Qing-Fu

2017-06-01

Container-molecules are attractive to chemists due to their unique structural characteristics comparable to enzymes and receptors in nature. We report here a family of artificial self-assembled macrocyclic containers that feature induced-fit transformations in response to different anionic guests. Five metal-organic macrocycles with empirical formula of MnL2n (M=Metal L=Ligand n=3, 4, 5, 6, 7) are selectively obtained starting from one simple benzimidazole-based ligand and square-planar palladium(II) ions, either by direct anion-adaptive self-assembly or induced-fit transformations. Hydrogen-bonding interactions between the inner surface of the macrocycles and the anionic guests dictate the shape and size of the product. A comprehensive induced-fit transformation map across all the MnL2n species is drawn, with a representative reconstitution process from Pd7L14 to Pd3L6 traced in detail, revealing a gradual ring-shrinking mechanism. We envisage that these macrocyclic molecules with adjustable well-defined hydrogen-bonding pockets will find wide applications in molecular sensing or catalysis.

Morphology versus Vertical Phase Segregation in Solvent Annealed Small Molecule Bulk Heterojunction Organic Solar Cells

Directory of Open Access Journals (Sweden)

Alexander Kovalenko

2015-01-01

Full Text Available The deep study of solvent annealed small molecules bulk heterojunction organic solar cells based on DPP(TBFu2 : PC60BM blend is carried out. To reveal the reason of the solvent annealing advantage over the thermal one, capacitance-voltage measurements were applied. It was found that controlling the vertical phase segregation in the solar cells a high fullerene population in the vicinity of the cathode could be achieved. This results in increase of the shunt resistance of the cell, thus improving the light harvesting efficiency.

Fluorescence based fiber optic and planar waveguide biosensors. A review

International Nuclear Information System (INIS)

Benito-Peña, Elena; Valdés, Mayra Granda; Glahn-Martínez, Bettina; Moreno-Bondi, Maria C.

2016-01-01

The application of optical biosensors, specifically those that use optical fibers and planar waveguides, has escalated throughout the years in many fields, including environmental analysis, food safety and clinical diagnosis. Fluorescence is, without doubt, the most popular transducer signal used in these devices because of its higher selectivity and sensitivity, but most of all due to its wide versatility. This paper focuses on the working principles and configurations of fluorescence-based fiber optic and planar waveguide biosensors and will review biological recognition elements, sensing schemes, as well as some major and recent applications, published in the last ten years. The main goal is to provide the reader a general overview of a field that requires the joint collaboration of researchers of many different areas, including chemistry, physics, biology, engineering, and material science. - Highlights: • Principles, configurations and fluorescence techniques using fiber optic and planar waveguide biosensors are discussed. • The biorecognition elements and sensing schemes used in fiber optic and planar waveguide platforms are reviewed. • Some major and recent applications of fiber optic and planar waveguide biosensors are introduced.

Fluorescence based fiber optic and planar waveguide biosensors. A review

Energy Technology Data Exchange (ETDEWEB)

Benito-Peña, Elena [Department of Analytical Chemistry, Faculty of Chemistry, Complutense University, 28040 Madrid (Spain); Valdés, Mayra Granda [Department of Analytical Chemistry, Faculty of Chemistry, University of La Habana, 10400 La Habana (Cuba); Glahn-Martínez, Bettina [Department of Analytical Chemistry, Faculty of Chemistry, Complutense University, 28040 Madrid (Spain); Moreno-Bondi, Maria C., E-mail: mcmbondi@quim.ucm.es [Department of Analytical Chemistry, Faculty of Chemistry, Complutense University, 28040 Madrid (Spain)

2016-11-02

The application of optical biosensors, specifically those that use optical fibers and planar waveguides, has escalated throughout the years in many fields, including environmental analysis, food safety and clinical diagnosis. Fluorescence is, without doubt, the most popular transducer signal used in these devices because of its higher selectivity and sensitivity, but most of all due to its wide versatility. This paper focuses on the working principles and configurations of fluorescence-based fiber optic and planar waveguide biosensors and will review biological recognition elements, sensing schemes, as well as some major and recent applications, published in the last ten years. The main goal is to provide the reader a general overview of a field that requires the joint collaboration of researchers of many different areas, including chemistry, physics, biology, engineering, and material science. - Highlights: • Principles, configurations and fluorescence techniques using fiber optic and planar waveguide biosensors are discussed. • The biorecognition elements and sensing schemes used in fiber optic and planar waveguide platforms are reviewed. • Some major and recent applications of fiber optic and planar waveguide biosensors are introduced.

Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities

Directory of Open Access Journals (Sweden)

Margaux eMesle

2015-06-01

Full Text Available Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich rocks, shales and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e. the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility of the carbon and energy source. Indeed, bitumen has a colloidal structure that may limit the accessibility to asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix.

Control of π-Electron Rotations in Chiral Aromatic Molecules Using Intense Laser Pulses

Science.gov (United States)

Kanno, Manabu; Kono, Hirohiko; Fujimura, Yuichi

Our recent theoretical studies on laser-induced π-electron rotations in chiral aromatic molecules are reviewed. π electrons of a chiral aromatic molecule can be rotated along its aromatic ring by a nonhelical, linearly polarized laser pulse. An ansa aromatic molecule with a six-membered ring, 2,5-dichloro[n](3,6) pyrazinophane, which belongs to a planar-chiral molecule group, and its simplified molecule 2,5-dichloropyrazine are taken as model molecules. Electron wavepacket simulations in the frozen-molecular-vibration approximation show that the initial direction of π-electron rotation depends on the polarization direction of a linearly polarized laser pulse applied. Consecutive unidirectional rotation can be achieved by applying a sequence of linearly polarized pump and dump pulses to prevent reverse rotation. Optimal control simulations of π-electron rotation show that another controlling factor for unidirectional rotation is the relative optical phase between the different frequency components of an incident pulse in addition to photon polarization direction. Effects of nonadiabatic coupling between π-electron rotation and molecular vibrations are also presented, where the constraints of the frozen approximation are removed. The angular momentum gradually decays mainly owing to nonadiabatic coupling, while the vibrational amplitudes greatly depend on their rotation direction. This suggests that the direction of π-electron rotation on an attosecond timescale can be identified by detecting femtosecond molecular vibrations.

Modeling and optimization of planar microcoils

International Nuclear Information System (INIS)

Beyzavi, Ali; Nguyen, Nam-Trung

2008-01-01

Magnetic actuation has emerged as a useful tool for manipulating particles, droplets and biological samples in microfluidics. A planar coil is one of the suitable candidates for magnetic actuation and has the potential to be integrated in digital microfluidic devices. A simple model of microcoils is needed to optimize their use in actuation applications. This paper first develops an analytical model for calculating the magnetic field of a planar microcoil. The model was validated by experimental data from microcoils fabricated on printed circuit boards (PCB). The model was used for calculating the field strength and the force acting on a magnetic object. Finally, the effect of different coil parameters such as the magnitude of the electric current, the gap between the wires and the number of wire segments is discussed. Both analytical and experimental results show that a smaller gap size between wire segments, more wire segments and a higher electric current can increase both the magnitude and the gradient of the magnetic field, and consequently cause a higher actuating force. The planar coil analyzed in the paper is suitable for applications in magnetic droplet-based microfluidics

Epithelial rotation is preceded by planar symmetry breaking of actomyosin and protects epithelial tissue from cell deformations.

Science.gov (United States)

Viktorinová, Ivana; Henry, Ian; Tomancak, Pavel

2017-11-01

Symmetry breaking is involved in many developmental processes that form bodies and organs. One of them is the epithelial rotation of developing tubular and acinar organs. However, how epithelial cells move, how they break symmetry to define their common direction, and what function rotational epithelial motions have remains elusive. Here, we identify a dynamic actomyosin network that breaks symmetry at the basal surface of the Drosophila follicle epithelium of acinar-like primitive organs, called egg chambers, and may represent a candidate force-generation mechanism that underlies the unidirectional motion of this epithelial tissue. We provide evidence that the atypical cadherin Fat2, a key planar cell polarity regulator in Drosophila oogenesis, directs and orchestrates transmission of the intracellular actomyosin asymmetry cue onto a tissue plane in order to break planar actomyosin symmetry, facilitate epithelial rotation in the opposite direction, and direct the elongation of follicle cells. In contrast, loss of this rotational motion results in anisotropic non-muscle Myosin II pulses that are disorganized in plane and causes cell deformations in the epithelial tissue of Drosophila eggs. Our work demonstrates that atypical cadherins play an important role in the control of symmetry breaking of cellular mechanics in order to facilitate tissue motion and model epithelial tissue. We propose that their functions may be evolutionarily conserved in tubular/acinar vertebrate organs.

Intermediate-Sized Conjugated Donor Molecules for Organic Solar Cells: Comparison of Benzodithiophene and Benzobisthiazole-Based Cores

KAUST Repository

Zhang, Siyuan

2017-09-05

Two intermediate-sized donor molecules, BBTz-X and BDT-X, have been synthesized by the Stille coupling between 4-(4,4-bis(2-ethylhexyl)-6-(trimethylstannyl)-4H-silolo[3,2-b:4,5-b′]dithiophen-2-yl)-7-(5′-hexyl-[2,2′-bithiophen]-5-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine and either 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-2,6-diiodobenzo[1,2-d:4,5-d′]bis(thiazole) or 2,6-dibromo-4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene, respectively. Both oxidation and reduction potentials for BBTz-X are anodically shifted relative to those for BDT-X, but the oxidation potential is more sensitive to the identity of the core; this is consistent with what is seen for DFT-calculated HOMO and LUMO energies and with a slightly blue-shifted absorption maximum for BBTz-X. Although DFT calculations, along with crystal structures of related compounds, suggest more planar molecular structures for BBTz-X than for BDT-X, film structures and the effects of various annealing processes on these films, as revealed by GIWAXS, are similar. The performance of BDT-X:PC61BM bulk-heterojunction solar cells is more sensitive to annealing conditions than that of BBTz-X:PC61BM cells, but under appropriate conditions, both yield power conversion efficiencies of >7%.

Intermediate-Sized Conjugated Donor Molecules for Organic Solar Cells: Comparison of Benzodithiophene and Benzobisthiazole-Based Cores

KAUST Repository

Zhang, Siyuan; Zhang, Junxiang; Abdelsamie, Maged; Shi, Qinqin; Zhang, Yadong; Parker, Timothy C.; Jucov, Evgheni V.; Timofeeva, Tatiana V.; Amassian, Aram; Bazan, Guillermo C.; Blakey, Simon B.; Barlow, Stephen; Marder, Seth R.

2017-01-01

Two intermediate-sized donor molecules, BBTz-X and BDT-X, have been synthesized by the Stille coupling between 4-(4,4-bis(2-ethylhexyl)-6-(trimethylstannyl)-4H-silolo[3,2-b:4,5-b′]dithiophen-2-yl)-7-(5′-hexyl-[2,2′-bithiophen]-5-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine and either 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-2,6-diiodobenzo[1,2-d:4,5-d′]bis(thiazole) or 2,6-dibromo-4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene, respectively. Both oxidation and reduction potentials for BBTz-X are anodically shifted relative to those for BDT-X, but the oxidation potential is more sensitive to the identity of the core; this is consistent with what is seen for DFT-calculated HOMO and LUMO energies and with a slightly blue-shifted absorption maximum for BBTz-X. Although DFT calculations, along with crystal structures of related compounds, suggest more planar molecular structures for BBTz-X than for BDT-X, film structures and the effects of various annealing processes on these films, as revealed by GIWAXS, are similar. The performance of BDT-X:PC61BM bulk-heterojunction solar cells is more sensitive to annealing conditions than that of BBTz-X:PC61BM cells, but under appropriate conditions, both yield power conversion efficiencies of >7%.

A GROMOS-Compatible Force Field for Small Organic Molecules in the Condensed Phase: The 2016H66 Parameter Set.

Science.gov (United States)

Horta, Bruno A C; Merz, Pascal T; Fuchs, Patrick F J; Dolenc, Jozica; Riniker, Sereina; Hünenberger, Philippe H

2016-08-09

This article reports on the calibration and validation of a new GROMOS-compatible parameter set 2016H66 for small organic molecules in the condensed phase. The calibration is based on 62 organic molecules spanning the chemical functions alcohol, ether, aldehyde, ketone, carboxylic acid, ester, amine, amide, thiol, sulfide, and disulfide, as well as aromatic compounds and nucleic-acid bases. For 57 organic compounds, the calibration targets are the experimental pure-liquid density ρliq and the vaporization enthalpy ΔHvap, as well as the hydration free energy ΔGwat and the solvation free energy ΔGche in cyclohexane, at atmospheric pressure and at (or close to) room temperature. The final root-mean-square deviations (RMSD) for these four quantities over the set of compounds are 32.4 kg m(-3), 3.5 kJ mol(-1), 4.1 kJ mol(-1), and 2.1 kJ mol(-1), respectively, and the corresponding average deviations (AVED) are 1.0 kg m(-3), 0.2 kJ mol(-1), 2.6 kJ mol(-1), and 1.0 kJ mol(-1), respectively. For the five nucleic-acid bases, the parametrization is performed by transferring the final 2016H66 parameters from analogous organic compounds followed by a slight readjustment of the charges to reproduce the experimental water-to-chloroform transfer free energies ΔGtrn. The final RMSD for this quantity over the five bases is 1.7 kJ mol(-1), and the corresponding AVED is 0.8 kJ mol(-1). As an initial validation of the 2016H66 set, seven additional thermodynamic, transport, and dielectric properties are calculated for the 57 organic compounds in the liquid phase. The agreement with experiment in terms of these additional properties is found to be reasonable, with significant deviations typically affecting either a specific chemical function or a specific molecule. This suggests that in most cases, a classical force-field description along with a careful parametrization against ρliq, ΔHvap, ΔGwat, and ΔGche results in a model that appropriately describes the liquid in terms of

Ambient mass spectrometry: From the planar to the non-planar surface analysis

Czech Academy of Sciences Publication Activity Database

Rejšek, Jan; Vrkoslav, Vladimír; Cvačka, Josef

2017-01-01

Roč. 15, č. 1 (2017), s. 31 ISSN 2336-7202. [Mezioborové setkání mladých biologů, biochemiků a chemiků /17./. 30.05.2017-01.06.2017, Milovy] Institutional support: RVO:61388963 Keywords : ambient mass spectrometry * thin layer chromatography * non-planar surface analysis Subject RIV: CB - Analytical Chemistry, Separation

SPECT versus planar bone radionuclide imaging in the detection of spondylolysis

International Nuclear Information System (INIS)

Whitten, C.G.; El-Khoury, G.Y.; Chang, P.J.; Seabold, J.E.; Found, E.M.; Renfrew, D.L.

1991-01-01

This paper evaluates the relative performance and ease of interpretation of SPECT versus planar radionuclide bone imaging in the detection of spondylolysis. The authors studied all patients presenting with back pain suggestive of spondylolysis from November 1989 to January 1991 who underwent bone scanning; patients underwent both planar and SPECT imaging. The planar and SPECT images were randomly mixed and independently interpreted by four observers for presence or absence of spondylolysis and ease of interpretation for each scan. Receiver operating characteristic (ROC) and analysis of variance (ANOVA) were used. Of 72 patients, 19 had confirmed spondylolysis, and 53 did not. While ROC analysis showed that SPECT performed slightly better than planar imaging for all four observers, the difference was not statistically significant. ANOVA results suggest that planar imaging was significantly easier to use than SPECT and that ease of use was strongly correlated with the observer's confidence in the diagnosis

Rapid degradation of the complex organic molecules in Martian surface rocks due to exposure to cosmic rays. Implications to the search of 'extinct' life on Mars by MSL and ExoMars

Science.gov (United States)

Pavlov, A.; Eigenbrode, J. L.; Glavin, D. P.; Floyd, M.; Mahaffy, P. R.

2013-12-01

Until recently, long-term exposure to cosmic rays has not been recognized as a major environmental factor, which can alter and destroy organic molecules in the Martian surface rocks. Recent modeling studies (e.g. Pavlov et al., 2012) suggested that organic molecules with masses >100 amu would be degraded in less than 1 billion years in the top 5 cm of the Martian rocks. That poses a serious challenge to the search of ancient molecules in the shallow subsurface of Mars. However, Pavlov et al. calculated the fraction of the survived organic molecules using conservative radiolysis constants derived from the gamma irradiation experiments on pure dry amino acid mixtures (Kminek and Bada, 2006). In this study we conducted a series of gamma irradiations of amino acids and carboxylic acids mixed with silica powder. We report that the addition of silicates dramatically increased the rate of organic degradation under gamma radiation. Using the newly derived radiolysis constants for amino acids and carboxylic acids in mineral mixtures, we recalculated the rate of organic degradation in the Martian rocks as a function of rocks' depth, chemical composition and weathering rates. Our results suggest that isolated organic molecules (acids) are likely to be altered or fully degraded in the surface rocks on Mars by cosmic rays in less than 10 million years unless some additional protective mechanisms are in place. We will discuss possible strategies for the MSL's search of the elusive ancient organic molecules to overcome the adverse effects of cosmic rays in the surface Martian rocks. References. Pavlov et al., 2012 GEOPHYSICAL RESEARCH LETTERS, doi:10.1029/2012GL052166 Kminek, G., and J. Bada (2006), Earth Planet. Sci. Lett., 245, 1-5, doi:10.1016/j.epsl.2006.03.008.

Electronic coupling effects and charge transfer between organic molecules and metal surfaces

Energy Technology Data Exchange (ETDEWEB)

Forker, Roman

2010-07-01

We employ a variant of optical absorption spectroscopy, namely in situ differential reflectance spectroscopy (DRS), for an analysis of the structure-properties relations of thin epitaxial organic films. Clear correlations between the spectra and the differently intense coupling to the respective substrates are found. While rather broad and almost structureless spectra are obtained for a quaterrylene (QT) monolayer on Au(111), the spectral shape resembles that of isolated molecules when QT is grown on graphite. We even achieve an efficient electronic decoupling from the subjacent Au(111) by inserting an atomically thin organic spacer layer consisting of hexa-peri-hexabenzocoronene (HBC) with a noticeably dissimilar electronic behavior. These observations are further consolidated by a systematic variation of the metal substrate (Au, Ag, and Al), ranging from inert to rather reactive. For this purpose, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) is chosen to ensure comparability of the molecular film structures on the different metals, and also because its electronic alignment on various metal surfaces has previously been studied with great intensity. We present evidence for ionized PTCDA at several interfaces and propose the charge transfer to be related to the electronic level alignment governed by interface dipole formation on the respective metals. (orig.)

Ice photochemistry as a source of amino acids and other organic molecules in meteorites, and implications for the origin of life and the search for life in the Solar System

Science.gov (United States)

Bernstein, Max

2005-01-01

The tons of extraterrestrial organic material that come to the Earth every day probably helped to made the Earth habitable, and possibly played a role in the origin of life. At the astrochemistry lab (http://www.astrochem.orq) we investigate the formation and distribution of organic molecules in space and consider the impact such molecules may have on the habitability of planets and the search for life in the Solar System. The organic compounds in meteorites include amino acids, aromatics of various sorts including purine and pyrimidine bases, and fatty acids that form bi-layer vesicles. The origin of many of these species remains mysterious, but in recent years we and others have performed experiments that suggest low temperature radiation chemistry could account for the presence and deuterium enrichment of many of these molecules. . I will present our laboratory experiments that show the viability of low temperature radiation chemistry as a source of organic molecules such as;amino acids (Nature, 2002, 416, 401-403), amphiphiles (Astrobiology, 2003, 2, 371, Proc. Nat. Acad. Sci. 2001, 98, 815), quinones (Science, 1999, 283, 1135) and other functionalized aromatic compounds (Meteoritics, 2001, 36, 351 ; Astrophysical Journal., 2003, 582, L25), some of which were invoked as potential biomarkers in the Alan Hills 84001 Martian meteorite. Understanding how components of proteins and DNA could form in sterile space environments is also of relevance to our search for life elsewhere in the Solar System, the great task now ahead of NASA. If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While most people think of molecules such as amino acids, and nucleo-bases as good candidate biomarkers, these molecules are produced non-biotically in space and are expected to be present on the surface of other planets even in the absence of

Medium-Bandgap Small-Molecule Donors Compatible with Both Fullerene and Nonfullerene Acceptors.

Science.gov (United States)

Huo, Yong; Yan, Cenqi; Kan, Bin; Liu, Xiao-Fei; Chen, Li-Chuan; Hu, Chen-Xia; Lau, Tsz-Ki; Lu, Xinhui; Sun, Chun-Lin; Shao, Xiangfeng; Chen, Yongsheng; Zhan, Xiaowei; Zhang, Hao-Li

2018-03-21

Much effort has been devoted to the development of new donor materials for small-molecule organic solar cells due to their inherent advantages of well-defined molecular weight, easy purification, and good reproducibility in photovoltaic performance. Herein, we report two small-molecule donors that are compatible with both fullerene and nonfullerene acceptors. Both molecules consist of an (E)-1,2-di(thiophen-2-yl)ethane-substituted (TVT-substituted) benzo[1,2-b:4,5-b']dithiophene (BDT) as the central unit, and two rhodanine units as the terminal electron-withdrawing groups. The central units are modified with either alkyl side chains (DRBDT-TVT) or alkylthio side chains (DRBDT-STVT). Both molecules exhibit a medium bandgap with complementary absorption and proper energy level offset with typical acceptors like PC 71 BM and IDIC. The optimized devices show a decent power conversion efficiency (PCE) of 6.87% for small-molecule organic solar cells and 6.63% for nonfullerene all small-molecule organic solar cells. Our results reveal that rationally designed medium-bandgap small-molecule donors can be applied in high-performance small-molecule organic solar cells with different types of acceptors.

Search for biochemical fossils on earth and non-biological organic molecules on Jupiter, Saturn and Titan

Science.gov (United States)

Nagy, Bartholomew

1982-07-01

Recognizable remnants of ancient biochemicals may survive under mild/moderate geological environments. Acyclic isoprenoid hydrocarbons, cyclic hydrocarbons with terpenoid carbon skeletons (e.g. hopanes) and vanadyl and nickel porphyrins have been isolated from organic matter, including petroleum, in Phanerozoic sedimentary rocks. Remnants of lignin have also been found. Usually, carbohydrates do not survive long; they degrade and/or react with other organic substances to form macromolecular matter. Proteins, e.g. apparently those in dinosaur bone collagen, break down relatively rapidly. Life arose during the Precambrian and potential biochemical fossils, e.g. n-alkanes, 2,5-dimethylfuran have been isolated from Precambrian kerogens. Traces of hydrocarbons, NH3, PH3 occur on Jupiter and Saturn. Hydrocarbons, N2 and HCN, the latter a key intermediary in the laboratory abiological syntheses of amino acids and nucleic acid bases, are present on Titan where life could not have evolved. Precursor abiological organic molecules of some complexity may have been synthesized on Titan and the Jovian planets.

The Rho GTPase Cdc42 regulates hair cell planar polarity and cellular patterning in the developing cochlea

Directory of Open Access Journals (Sweden)

Anna Kirjavainen

2015-03-01

Full Text Available Hair cells of the organ of Corti (OC of the cochlea exhibit distinct planar polarity, both at the tissue and cellular level. Planar polarity at tissue level is manifested as uniform orientation of the hair cell stereociliary bundles. Hair cell intrinsic polarity is defined as structural hair bundle asymmetry; positioning of the kinocilium/basal body complex at the vertex of the V-shaped bundle. Consistent with strong apical polarity, the hair cell apex displays prominent actin and microtubule cytoskeletons. The Rho GTPase Cdc42 regulates cytoskeletal dynamics and polarization of various cell types, and, thus, serves as a candidate regulator of hair cell polarity. We have here induced Cdc42 inactivation in the late-embryonic OC. We show the role of Cdc42 in the establishment of planar polarity of hair cells and in cellular patterning. Abnormal planar polarity was displayed as disturbances in hair bundle orientation and morphology and in kinocilium/basal body positioning. These defects were accompanied by a disorganized cell-surface microtubule network. Atypical protein kinase C (aPKC, a putative Cdc42 effector, colocalized with Cdc42 at the hair cell apex, and aPKC expression was altered upon Cdc42 depletion. Our data suggest that Cdc42 together with aPKC is part of the machinery establishing hair cell planar polarity and that Cdc42 acts on polarity through the cell-surface microtubule network. The data also suggest that defects in apical polarization are influenced by disturbed cellular patterning in the OC. In addition, our data demonstrates that Cdc42 is required for stereociliogenesis in the immature cochlea.

Synthesis of Sub-10 nm Two-Dimensional Covalent Organic Thin Film with Sharp Molecular Sieving Nanofiltration

KAUST Repository

Gadwal, Ikhlas

2018-04-06

We demonstrated here a novel and facile synthesis of two-dimensional (2D) covalent organic thin film with pore size around 1.5 nm using a planar, amphiphilic and substituted heptacyclic truxene based triamine and a simple dialdehyde as building blocks by dynamic imine bond formation at the air/water interface using Langmuir–Blodgett (LB) method. Optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM), all unanimously showed the formation of large, molecularly thin and free-standing membrane that can be easily transferred on different substrate surfaces. The 2D membrane supported on a porous polysulfone showed a rejection rate of 64 and 71% for NaCl and MgSO4, respectively, and a clear molecular sieving at molecular size around 1.3 nm, which demonstrated a great potential in the application of pretreatment of seawater desalination and separation of organic molecules.

Inorganics in Organics: Tracking down the Intrinsic Equilibriums between Organic Molecules and Trace Elements in Oceanic Waters

Science.gov (United States)

Lechtenfeld, O. J.; Koch, B. P.; Kattner, G.

2010-12-01

Recent developments in analytical instrumentation enable to describe biogeochemical processes in oceanic waters on a molecular level. This is the prerequisite to integrate biological and geochemical parameters and to develop chemical cycles on a global perspective. The state-of-the-art Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) applications for dissolved organic matter (DOM) focus mainly on carbon, hydrogen, oxygen and nitrogen isotopes. Implementation of sulfur and especially phosphorus in the molecular formula assignment has been questionable because of ambiguous calculated elemental formulas. On the other hand, many compounds bearing these elements are well known to occur in the dissolved state as part of the permanent recycling processes (e.g. phospholipids, phosphonates) but analytics of dissolved organic phosphorus (DOP) and sulfur (DOS) are often hampered by the large inorganic P and S pools. Even less is known about complexation characteristics of the DOM moieties. Although electrochemical methods provide some information about trace metal speciation, the high amount of organic molecules and its insufficient description as chemical functional classes prevent the assignment of trace metals to ligand classes. Nevertheless, it is undoubtful that a varying but extensive amount of transition metals is bond in form of organic complexes. Hyphenation of reversed phase high performance liquid chromatography (RP-HPLC) with high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) is a valuable tool to study these metal-organic interactions in a qualitative and quantitative approach. We established a desolvation method that allows direct transfer of high organic solvent loads into the plasma. Thus, in combination with internal standardization and external calibration, the investigation of a broad polarity scale was possible. This approach overcomes previous restrictions to non-organic solvent separation techniques like size

The value of filtered planar images in pediatric DMSA scans

International Nuclear Information System (INIS)

Mohammed, A.M.; Naddaf, S.Y.; Elgazzar, A.H.; Al-Abdul Salam, A.A.; Omar, A.A.

2006-01-01

The study was designed to demonstrate the value of filtered planar images in paediatric DMSA scanning. One hundred and seventy three patients ranged in age from 15 days to 12 years (mean: 4.3 years) with urinary tract infection (UTI) and clinical and/or laboratory suspicion of acute pyelonephritis (APN) were retrospectively studied. Planar images were filtered using Butterworth filter. The scan findings were reported as positive, negative or equivocal for cortical defects. Each scan was read in a double-blind fashion by two nuclear medicine physicians to evaluate inter-observer variations. Each kidney was divided into three zones, upper, middle and lower, and each zone was graded as positive, negative or equivocal for the presence of renal defects. Renal cortical defects were found in 66 patients (91 kidneys and 186 zones) with filtered images, 58 patients (81 kidneys and 175 zones) with planar images, and 69 patients (87 kidneys and 180 zones) with SPECT images. McNemar's test revealed statistically significant difference between filtered and planar images (p=0.038 for patients, 0.021 for kidneys and 0.034 for number of zones). Inter-observer agreement was 0.877 for filtered images, 0.915 for planar images and 0.915 for SPECT images. It was concluded that filtered planar images of renal cortex are comparable to SPECT images and can be used effectively in place of SPECT, when required, to shorten imaging time and eliminate motion artifacts, especially in the paediatric population. (author)

Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm 2/Vs

KAUST Repository

Smith, Jeremy N.; Zhang, Weimin; Sougrat, Rachid; Zhao, Kui; Li, Ruipeng; Cha, Dong Kyu; Amassian, Aram; Heeney, Martin J.; McCulloch, Iain A.; Anthopoulos, Thomas D.

2012-01-01

Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm 2/Vs, current on/off ratio ≥10 6 and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solution-processed small molecule-polymer blend organic thin-film transistors with hole mobility greater than 5 cm 2/Vs

KAUST Repository

Smith, Jeremy N.

2012-04-10

Using phase-separated organic semiconducting blends containing a small molecule, as the hole transporting material, and a conjugated amorphous polymer, as the binder material, we demonstrate solution-processed organic thin-film transistors with superior performance characteristics that include; hole mobility >5 cm 2/Vs, current on/off ratio ≥10 6 and narrow transistor parameter spread. These exceptional characteristics are attributed to the electronic properties of the binder polymer and the advantageous nanomorphology of the blend film. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling and analysis of a novel planar eddy current damper

Science.gov (United States)

Zhang, He; Kou, Baoquan; Jin, Yinxi; Zhang, Lu; Zhang, Hailin; Li, Liyi

2014-05-01

In this paper, a novel 2-DOF permanent magnet planar eddy current damper is proposed, of which the stator is made of a copper plate and the mover is composed of two orthogonal 1-D permanent magnet arrays with a double sided structure. The main objective of the planar eddy current damper is to provide two orthogonal damping forces for dynamic systems like the 2-DOF high precision positioning system. Firstly, the basic structure and the operating principle of the planar damper are introduced. Secondly, the analytical model of the planar damper is established where the magnetic flux density distribution of the permanent magnet arrays is obtained by using the equivalent magnetic charge method and the image method. Then, the analytical expressions of the damping force and damping coefficient are derived. Lastly, to verify the analytical model, the finite element method (FEM) is adopted for calculating the flux density and a planar damper prototype is manufactured and thoroughly tested. The results from FEM and experiments are in good agreement with the ones from the analytical expressions indicating that the analytical model is reasonable and correct.

Dynamical analysis of surface-insulated planar wire array Z-pinches

Science.gov (United States)

Li, Yang; Sheng, Liang; Hei, Dongwei; Li, Xingwen; Zhang, Jinhai; Li, Mo; Qiu, Aici

2018-05-01

The ablation and implosion dynamics of planar wire array Z-pinches with and without surface insulation are compared and discussed in this paper. This paper first presents a phenomenological model named the ablation and cascade snowplow implosion (ACSI) model, which accounts for the ablation and implosion phases of a planar wire array Z-pinch in a single simulation. The comparison between experimental data and simulation results shows that the ACSI model could give a fairly good description about the dynamical characteristics of planar wire array Z-pinches. Surface insulation introduces notable differences in the ablation phase of planar wire array Z-pinches. The ablation phase is divided into two stages: insulation layer ablation and tungsten wire ablation. The two-stage ablation process of insulated wires is simulated in the ACSI model by updating the formulas describing the ablation process.

Anisotropic Magnus Force in Type-II Superconductors with Planar Defects

Science.gov (United States)

Monroy, Ricardo Vega; Gomez, Eliceo Cortés

2015-02-01

The effect of planar defects on the Magnus force in type-II superconductors is studied. It is shown that the deformation of the vortex due to the presence of a planar defect leads to a local decrease in the mean free path of electrons in the vortex. This effect reduces the effective Magnus coefficient in normal direction to the planar defect, leading to an anisotropic regime of the Hall effect. The presented developments here can qualitatively explain experimental observations of the anisotropic Hall effect in high- T c superconductors in the mixed state.

First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

Energy Technology Data Exchange (ETDEWEB)

Mann, Gregory W., E-mail: gmann@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Mesosphere, Inc., San Francisco, California 94105 (United States); Lee, Kyuho, E-mail: kyuholee@lbl.gov [Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Synopsys, Inc., Mountain View, California 94043 (United States); Cococcioni, Matteo, E-mail: matteo.cococcioni@epfl.ch [Theory and Simulation of Materials (THEOS), École Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Smit, Berend, E-mail: Berend-Smit@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720 (United States); Laboratory of Molecular Simulation, Institut des Sciences et Ingénierie Chimiques, Valais Ecole Polytechnique Fédérale de Lausanne (EPFL), Rue de l’Industrie 17, CH-1951 Sion (Switzerland); Neaton, Jeffrey B., E-mail: jbneaton@lbl.gov [Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Physics, University of California, Berkeley, California 94720 (United States); Kavli Energy NanoSciences Institute at Berkeley, Berkeley, California 94720 (United States)

2016-05-07

We apply first-principles approaches with Hubbard U corrections for calculation of small molecule binding energetics to open-shell transition metal atoms in metal-organic frameworks (MOFs). Using density functional theory with van der Waals dispersion-corrected functionals, we determine Hubbard U values ab initio through an established linear response procedure for M-MOF-74, for a number of different metal centers (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu). While our ab initio U values differ from those used in previous work, we show that they result in lattice parameters and electronic contributions to CO{sub 2}-MOF binding energies that lead to excellent agreement with experiments and previous results, yielding lattice parameters within 3%. In addition, U-dependent calculations for an example system, Co-MOF-74, suggest that the CO{sub 2} binding energy grows monotonically with the value of Hubbard U, with the binding energy shifting 4 kJ/mol (or 0.041 eV) over the range of U = 0-5.4 eV. These results provide insight into an approximate but computationally efficient means for calculation of small molecule binding energies to open-shell transition metal atoms in MOFs and suggest that the approach can be predictive with good accuracy, independent of the cations used and the availability of experimental data.

First-principles Hubbard U approach for small molecule binding in metal-organic frameworks

International Nuclear Information System (INIS)