Systematic Analysis of Polymer Molecular Weight Influence on the Organic Photovoltaic Performance

The molecular weight of an electron donor‐conjugated polymer is as essential as other well‐known parameters in the chemical structure of the polymer, such as length and the nature of any side groups (alkyl chains) positioned on the polymeric backbone, as well as their placement, relative strength, the ratio of the donor and acceptor moieties in the backbone of donor–acceptor (D–A)‐conjugated polymers, and the arrangement of their energy levels for organic photovoltaic performance. Finding the “optimal” molecular weight for a specific conjugated polymer is an important aspect for the development of novel photovoltaic polymers. Therefore, it is evident that the chemistry of functional conjugated polymers faces major challenges and materials have to adopt a broad range of specifications in order to be established for high photovoltaic performance. In this review, the approaches followed for enhancing the molecular weight of electron‐donor polymers are presented in detail, as well as how this influences the optoelectronic properties, charge transport properties, structural conformation, morphology, and the photovoltaic performance of the active layer.

     

Evaluation of Lighting Systems,Carbon Sources,and Bacteria Cultures on Photofermentative Hydrogen Production

Fluorescent and incandescent lighting systems were applied for batch photofermentative hydrogen production by four purple non-sulfur photosynthetic bacteria (PNSB). The hydrogen production efficiency of Rhodopseudomonas palustris, Rhodobacter sphaeroides, Rhodobacter capsulatus, and Rhodospirillum rubrum was evaluated using different carbon sources (acetate, butyrate, lactate, and malate). Incandescent light was found to be more effective for bacteria cell growth and hydrogen production. It was observed that PNSB followed substrate selection criteria for hydrogen production. Only R. palustris was able to produce hydrogen using most carbon sources. Cell density was almost constant, but cell growth rate and hydrogen production were significantly varied under the different lighting systems. The kinetics study suggested that initial substrate concentration had a positive correlation with lag phase duration. Among the PNSB, R. palustris grew faster and had higher hydrogen yields of 1.58, 4.92, and 2.57 mol H₂/mol using acetate, butyrate, and lactate, respectively. In the integrative approach with dark fermentation effluents rich in organic acids, R. palustris should be enriched in the phototrophic microbial consortium of the continuous hydrogen production system.     

Ferrimagnetic ceramic adsorbents for cleanup of H2S from exhaust gases

Adsorbents that exhibit magnetic properties in addition to other required process-relevant characteristics open up new perspectives for the dry reduction and/or elimination of HES and other sulfur compounds from exhaust gases. These adsorbents eliminate the sulfur compounds from exhaust gases by virtue of their coatings and their magnetic property which makes it possible the use of magnetically assisted and stabilized fluidization in an externally applied magnetic field. In the present paper, the feasibility of the sorptive function of porous ceramic ferrimagnetic beads is ensured by sol-gel coating of zinc oxide without the formation of Zn-Fe-oxides and without considerable decrease of available pore volume. The results of material characterization by SEM, Auger electron spectroscopy, X-ray and mercury-porosity measurements and the loading capacity of a HES/N2 model gas are presented and discussed. The resulting HES loading of the functionalized adsorbent beads is more than 10 times larger than that of the starting material. @ 2007 Chinese Society of Particuolo~v and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V.     

Synthesis,molecular, and morphological characterization of initial and modified diblock copolymers with organic acid chloride derivatives

Six well defined PS‐b‐PB_1,2 diblock copolymers (PS: polystyrene and PB: polybutadiene) with almost 100% of 1,2 microstructure for the PB segment were synthesized. Size exclusion chromatography (SEC), membrane osmometry (MO) and proton nuclear magnetic resonance spectroscopy (¹H NMR) were used for verification of the molecular characteristics and the 100% ‐1,2 addition for the PB blocks. Modification with heptanoyl or pentadecafluorooctanoyl chloride was accomplished via hydroboration and subsequent oxidation, leading to hydroxylated PB blocks and was verified with ¹H NMR and Fourier transform infrared (FTIR) spectroscopy. Only two samples were modified with both organic acid chloride derivatives. Structural characterization was accomplished via transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS) in all cases. The self‐assembly was more evident in the modified copolymers with the corresponding halides due to the increase of the molecular weight of the modified PB block. Taking into consideration the χN values in each case and comparing the results with those of PS‐b‐PI copolymers already reported in the literature the discrepancies with the theoretical predictions are very small or minimal. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Theoretical investigation of flame propagation through compositionally stratified methane–air mixtures

Flame propagation speeds in compositionally stratified methane–air mixtures were theoretically calculated as a function of the equivalence ratio distribution in the unburnt mixture and compared with experimental results. A solution of non-adiabatic flame propagation under a quasi-steady approximation was able qualitatively to describe the experimentally observed characteristics of flame speeds in stratified mixtures, which were flame speed increase in the vicinity of the flammability limits as well as for high equivalence ratio gradients. However, this analysis failed to provide quantitative agreement with the experimental results. In order to address this, the cumulative heat support effects on flame temperature, depending on the history of flame propagation, had to be accounted for. Quantitative agreement with the experiments was achieved, especially for propagation in lean mixtures.     

Synthesis and chemical modification of magnetic nanoparticles covalently bound to polystyrene-SiCl2-poly(2-vinylpyridine)

The present article offers a new approach to create a multifunctional material based on magnetic nanoparticles, which can be dispersed in aqueous and organic media. The preparation of this material was performed by binding covalently polymer chains based on a reactive diblock-copolymer of the polystyrene-SiCl₂-poly(2-vinylpyridine) type, with average molecular weight per number (M_n) equal to 14,700 g/mol and a polydispersity index (PDI) less than 1.1, onto the surface of γ-Fe₂O₃ magnetic nanoparticles. The dichlorosilane moiety of the diblock-copolymer reacted with the  OH groups of the magnetic nanoparticles immobilizing the polymer chain onto its surface. This reaction was monitored by FTIR and the polymer grafting density was determined by TGA and BET. Dynamic light scattering revealed that the hydrodynamic diameter of the nanoparticles increased after immobilizing the polymer. Contact angle measurements demonstrated the ability of the hybrid material to interact with organic and aqueous media allowing its dispersion in solvents with different polarities. This property was used to prepare a magnetically active emulsion. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1668–1675, 2010     

Matchings in simplicial complexes, circuits and toric varieties

Using a generalized notion of matching in a simplicial complex and circuits of vector configurations, we compute lower bounds for the minimum number of generators, the binomial arithmetical rank and the A-homogeneous arithmetical rank of a lattice ideal. Prime lattice ideals are toric ideals, i.e. the defining ideals of toric varieties.     

Hydrodynamic properties of A8B8 type miktoarm (Vergina) stars

The dilute solution properties of three (PS)₈(PI)₈ miktoarm (Vergina) stars were investigated by viscometry and dynamic light scattering in toluene and tetrahydrofuran (THF) (common good solvents), cyclohexane at 34.5°C (theta solvent for PS and good for PI) and dioxane at 34°C (theta solvent for PI and good for PS). Experimental intrinsic viscosity [η] and hydrodynamic radii, R_h, values in all solvents were larger for the miktoarm stars in comparison to the calculated ones using a simple model which describes the size of the copolymers as a weighted average of the sizes of the homopolymer stars with the same total molecular weight and number of arms as the copolymer. This expansion is discussed on the basis of the increased number of heterocontacts, the topological constrains imposed by the common junction point in this highly branched miktoarm architecture and the asymmetry in molecular weights of the different kinds of arms. The conformation adopted in dilute solutions can explain, to some extent, the morphological results obtained on the same materials. The ratios of viscometric to hydrodynamic radii are consistent with previous investigations on linear and star polymers and in accord with the hard sphere model. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1329–1335, 1999     

Dielectric studies of polymer-water interactions and water organization in PEO/water systems

We report the results of detailed investigations of polymer-water interactions and of the organization of water in the poly(ethylene oxide) (PEO)/water system by dielectric techniques. They include thermally stimulated depolarization currents (TSDC) techniques in the temperature range of 77-300 K and broadband dielectric relaxation spectroscopy (DRS) techniques of frequencies, 5 Hz-10 GHz, and temperatures, 173-300 K. The water content h was varied between 0 and 1.21 (grams of water per gram of dry PEO). The secondary γ mechanism of PEO and the reorientation of absorbed water molecules were extensively studied. The γ mechanism was found to be plasticized up to water contents of about 0.20. The reorientation of water molecules was studied in three different experiments and frequency/temperature regions. The results suggest strong interactions in the PEO/water system and indicate the presence of a separate water phase at high water contents. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1545–1560, 1997