Department of Chemistry

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CrystEngComm

Isomorphic Co (ii) and Zn (ii) phosphonates: co-crystal formation of [\{M 2 ($\eta$ 1-DMPzH) 4 (Cl 3 CPO 3) 2\}\{M ($\eta$ 1-DMPzH) 2 Cl 2\} 2](toluene) 2 (M= Co (ii) and Zn (ii))

Polymer solar cell modules were prepared directly on thin flexible barrier polyethylene terephthalate foil. The performance of the modules was found to be scalable from a single cell with an area of 6 cm2 to modules with a total area of up to 186 cm2. The substrate thickness was also explored and the performance was found to be independent of thickness in the range of 20-130 μm. The thinner substrates were found to present some challenge regarding handling but were not limited in performance. Large area modules on a substrate thickness of 45 μm were finally prepared by full roll-to-roll processing employing P3HT:PCBM as the active material and were found to exhibit a total area efficiency of &gt;1% (1000 W/m-2; AM1.5G) with a typical active-area efficiency in the 1.5-1.6% for total module area of &gt;110 cm2 due to high fill factors in excess of 50%. The modules were also found to have an active-area efficiency of &gt;1% under low light levels (∼100 W m-2). The modules were then subjected to extensive stability testing for a minimum of 1000 h employing several ISOS protocols. The modules presented higher than 80% of the initial performance (T80) in the dark (ISOS-D-1), in dark under elevated temperature of 65°C (ISOS-D-2), under low light (ISOS-LL), under full sunlight (ISOS-L-2), and under outdoor testing (ISOS-O), which was conducted in two locations in India and Denmark. We estimate maximum T80 for those tests to be 2800, 5000, 1300, 1000, and 3500 h respectively. The modules showed significant sensitivity to high humidity and had low values for T80 for dark storage tests at 50°C/85%RH (ISOS-D-3) and accelerated operation conditions with 0.7 sun/65 oC/50%RH (ISOS-L-3). We found the modules to be particularly suited for information and communications technology (ICT) and mobile applications where low humidity (&lt;50%) and lower temperatures (&lt;65°C) can be anticipated and we estimate operational lifetimes in excess of 1 year. © 2012 Elsevier B.V. All rights reserved.

Organic Electronics

Scalability and stability of very thin, roll-to-roll processed, large area, indium-tin-oxide free polymer solar cell modules

As solar cell modules are becoming larger, it is important to pay attention to defects originating from the fabrication process and degradation during operation in the ambient. In this article, a simple method of using computer screen display as a light source to map the photoresponse of the solar cells, is reported. The method requires only a conventional computer loaded with a software code that enables a light spot of defined size to raster scan across the cell area as the photogenerated voltage is read out by a voltmeter using a USB connection. Screen-display-induced photoresponse (SDIP) mapping is an enabling technique to reveal the defective regions in the active layer as well as at the electrode interface, which, in many instances, cannot be deciphered simply by visual examination. Spectral response mapping by using light spots of different colors is also possible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Energy Technology

Screen-Display-Induced Photoresponse Mapping for Large-Area Photovoltaics

Time-resolved confocal microscopy has been applied to study the cytoplasm and nucleus region of a single live Chinese hamster ovary (CHO) cell. To select the cytoplasm and the nucleus region, two different fluorescent probes are used. A hydrophobic fluorescent dye, DCM, localizes preferentially in the cytoplasm region of a CHO cell. A DNA binding dye, DAPI, is found to be inside the nucleus of the cell. The locations of the probes are clearly seen in the image. Emission maxima of the dyes (DCM in cytoplasm and DAPI in the nucleus) are compared to those of the same dyes in different solvents. From this, it is concluded that the polarity (dielectric constant, ε) of the microenvironment of DCM in the cytoplasm is ∼15. The nucleus is found to be much more polar with ε ≈ 60 (as reported by DAPI). The diffusion coefficient (and hence viscosity) in the cytoplasm and the nucleus was determined using fluorescence correlation spectroscopy (FCS). The diffusion coefficient (Dt) of the dye (DCM) in the cytoplasm is 2 μm 2 s-1 and is ∼150 times slower than that in bulk water (buffer). Dt of DAPI in the nucleus (15 μm2 s -1) is 30 times slower than that in bulk water (buffer). The extremely slow diffusion inside the cell has been ascribed to higher viscosity and also to the binding of the probes (DCM and DAPI) to large biological macromolecules. The solvation dynamics of water in the cytoplasm (monitored by DCM) exhibits an average relaxation time âŸ̈τsolof 1250 ± 50 ps, which is about 1000 times slower than in bulk water (1 ps). The solvation dynamics inside the nucleus (studied using DAPI) is about 2-fold faster, âŸ̈τsol ≈ 775 ps. The higher polarity, faster diffusion, and faster solvation dynamics in the nucleus indicates that it is less crowded and less restricted than the cytoplasm. © 2013 American Chemical Society.

Langmuir

Solvation dynamics of biological water in a single live cell under a confocal microscope

The List-Barbas-Mannich reaction of ethyl (p-methoxyphenylimino)acetate (p-methoxyphenyl = PMP) with unmodified aldehydes or ketones catalyzed by modularly designed organocatalysts (MDOs) that are self-assembled from proline and cinchona alkaloid thioureas (such as a quinidine-derived thiourea) produces the corresponding γ-oxo-α-amino acid derivatives in high yields and excellent stereoselectivities. No solvent is necessary for this reaction. Aldehydes are especially good substrates for this reaction: The reaction takes only a few minutes to yield the corresponding List-Barbas-Mannich products in excellent dr (up to >99:1) and ee values (up to >99% ee). © 2013 American Chemical Society.

Journal of Organic Chemistry

List-Barbas-Mannich reaction catalyzed by modularly designed organocatalysts

Department of Physics

Physical Review A - Atomic, Molecular, and Optical Physics

Erratum: Optimal quantum communication using multiparticle partially entangled states (Physical Review A - Atomic, Molecular, and Optical Physics (2013) 87 (022307))

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. © 2013 American Physical Society.

Physical Review Letters

Simulation of influence of bilayer melting on dynamics and thermodynamics of interfacial water

Crystal growth \& design

{Reactions of (E)-5-(Pyridin-4-yl-methyleneamino)isophthalic Acid (LH2) with Triorganotin Oxides and −Chloride. Formation of One-Dimensional- and Two {\ldots}}

A simple and efficient direct radical arylation of unactivated arenes is described which uses cheap and commercially available phenyl hydrazine as an initiator. The reaction occurs through a base promoted homolytic aromatic substitution (BHAS) mechanism involving aryl radicals and aryl radical anions as intermediates and offers a practical approach for preparation of an array of substituted biaryls. © 2013 American Chemical Society.

Fulltext

Organic Letters

Phenyl hydrazine as initiator for direct arene C-H arylation via base promoted homolytic aromatic substitution

Organocatalytic conjugate addition of thioacetic acid to a series of a-substituted N-acryloyloxazolidin-2- ones followed by enantioselective protonation has been studied in the presence of thiourea catalysts derived from cinchona alkaloids. Conjugate addition/protonation adducts have been obtained up to 97% ee and high yields. The methodology could serve as an easy and practical route to the syntheses of useful biologically active molecules. © 2013 Elsevier Ltd. All rights reserved.