Photo‐induced Charge Transfer and Relaxation of Persistent Charge Carriers in Polymer/Nanocrystal Composites for Applications in Hybrid Solar Cells

The photo‐induced charge transfer and the dynamics of persistent charge carriers in blends of semiconducting polymers and nanocrystals are investigated. Regioregular poly(3‐hexylthiophene) (P3HT) is used as the electron donor material, while the acceptor moiety is established by CdSe nanocrystals (nc‐CdSe) prepared via colloidal synthesis. As a reference system, organic blends of P3HT and [6,6]‐phenyl C₆₁‐butyric acid methyl ester (PCBM) are studied as well. The light‐induced charge transfer between P3HT and the acceptor materials is studied by photoluminescence (PL), photo‐induced absorption (PIA) and light‐induced electron spin resonance spectroscopy (LESR). Compared to neat P3HT samples, both systems show an intensified formation of polarons in the polymer upon photo‐excitation, pointing out successful separation of photogenerated charge carriers. Additionally, relaxation of the persistent charge carriers is investigated, and significant differences are found between the hybrid composite and the purely organic system. While relaxation, reflected in the transient signal decay of the polaron signal, is fast in the organic system, the hybrid blends exhibit long‐term persistence. The appearance of a second, slow recombination channel indicates the existence of deep trap states in the hybrid system, which leads to the capture of a large fraction of charge carriers. A change of polymer conformation due to the presence of nc‐CdSe is revealed by low temperature LESR measurements and microwave saturation techniques. The impact of the different recombination behavior on the photovoltaic efficiency of both systems is discussed.     

Lipid oxidation products of heated soybeans as a possible cause of protection from ruminal biohydrogenation

Heating oilseeds has been shown to improve the milk fatty acid profile when given to dairy cows, compared to raw oilseeds. However, results from published studies are conflicting. The conditions of heating and storage of the oilseeds could be responsible for these differences, probably partly through their effects on lipid oxidation, the products of which could act on ruminal biohydrogenation (BH). Thus, 15 different treatments were applied to ground soybeans: three levels of heating (no heating, 30 min at 110 or 150°C) × 5 ambient storage durations (0, 1, 2, 4, or 6 months). Soybeans were incubated in vitro with ruminal fluid for 6 h. Triacylglycerol (TAG) polymers, hydroperoxides and hydroxyacids (HOA), aldehydes, and fatty acids were assayed in soybeans and ruminal culture. No TAG polymer was detected in any treatment. Soybeans stored for a long time had a high content of HOA, whereas those heated at 150°C, whatever the storage duration, had high aldehyde contents. The percentage disappearance of cis‐9,cis‐12 18:2 and cis‐9,cis‐12,cis‐15 18:3 in incubates decreased significantly in cultures with heated soybeans, especially at 150°C, suggesting that this partial protection of polyunsaturated fatty acids (PUFA) from BH was at least in part linked to the aldehyde content of the heated soybeans. Practical applications: Oilseeds given to ruminants are often heated, and heat treatment is known to generate oxidation products. Knowing what oxidation products influence ruminal biohydrogenation of unsaturated fatty acids could result in technological processes allowing a better transfer of unsaturated fatty acids from oilseeds to ruminant products.     

1‐Arylsulfonyl‐5‐(N‐hydroxyacrylamide)indolines Histone Deacetylase Inhibitors Are Potent Cytokine Release Suppressors

A series of 1‐arylsulfonyl‐5‐(N‐hydroxyacrylamide)indolines ( 7 – 15 ) has been developed; the compounds exhibited potent histone deacetylase (HDAC) inhibitory activities. Notably, almost all of this series exhibited better HDAC‐inhibitory and antiproliferative activities than 3‐(1‐benzenesulfonyl‐1H‐indol‐5‐yl)‐N‐hydroxyacrylamide ( 6 ), as reported in a previous study. Among these compounds, 3‐[1‐(4‐methoxybenzenesulfonyl)‐2,3‐dihydro‐1H‐indol‐5‐yl]‐N‐hydroxyacrylamide ( 9 ) showed a two‐ to tenfold increase in activity compared to SAHA ( 1 ) in the suppression of lipopolysaccharide‐induced cytokine production. Compound 9 also caused a marked reduction in carrageenan‐induced acute inflammation in a rat model. Taken together, these data indicated that 1‐arylsulfonyl‐5‐(N‐hydroxyacrylamide)indolines HDAC inhibitors exhibit potent anti‐inflammatory activity.     

Synthesis and decomposition performance of a polymeric foaming agent containing a sulfonyl hydrazide moiety

A new monomer, methacryloyloxybis(benzenesulfonyl hydrazide) (MAOBSH) containing a foamable sulfonyl hydrazide functional group after decomposition by heating, was synthesized from 4,4′‐oxybis(benzenesulfonyl hydrazide) (OBSH) with methacryloyl chloride, and used to obtain poly(MAOBSH) as a polymeric foaming agent (PFA) in dry tetrahydrofuran at 70 °C using azobisisobutyronitrile as an initiator. The structures of the synthesized MAOBSH and poly(MAOBSH) were identified using Fourier transform infrared and ¹ H NMR spectroscopies. The decomposition temperature of poly(MAOBSH) was determined to be 245 °C and this temperature was decreased to around 160 °C by adding an activator such as surface‐treated urea to the polymer. The exothermic temperature and heat determined by the decomposition of the polymer were 256 °C and 287 J g^?1. The amount of gas evolution for poly(MAOBSH) measured at the decomposition temperature was 74 mL g^?1. Furthermore, polymers incorporating the PFA showed better skin and finer cell structure as well as better mechanical properties such as elongation and compression set than polymers with added OBSH due to the better compatibility of the developed PFA with polymers. © 2012 Society of Chemical Industry