Binary and Ternary Polymer Solar Cells Based on a Wide Bandgap D-A Copolymer Donor and Two Nonfullerene Acceptors with Complementary Absorption Spectral.

A new wide-bandgap conjugated D-A polymer denoted as P106 with a medium acceptor dithieno [2,3-e;3'2'-g]isoindole-7,9 (8H) (DTID) unit and strong 2-dodecylbenzo[1,2-b:3,4-b':6,5-b"]trithiophene (3TB) donor units shows an optical bandgap of 2.04 and highest occupied molecular orbital energy level of -5.56 eV. P106 is used as the donor and two nonfullerene acceptors-medium bandgap DBTBT-IC and narrow band Y18-DMO-are used as acceptors for the construction of binary and ternary bulk heterojunction polymer solar cells. The optimized polymer solar cells based on P106 : DBTBT-IC and P106 : Y18-DMO exhibit power conversion efficiencies of 11.76 % and 14.07 %, respectively. The short-circuit current density (22.78 mA cm-2 ) for the P106 : Y18-DMO device is higher than that for P106 : DBTBT-IC (18.56 mA cm-2 ) one, which could be attributed to the more photon harvesting efficiency of the P106 : Y18-DMO active layer. In light of the high short-circuit current densities and fill factors for the Y18-DMO based device and the high value of open circuit voltage of the DBTBT-IC based device, ternary polymer solar cells are fabricated by using ternary active layer (P106 : DBTBT-IC : Y18-DMO) and achieve a power conversion efficiency of 16.49 % with low energy loss of 0.47 eV.

Systemic suppression of the contact hypersensitivity by the products of protoporphyrin IX photooxidation.

Photodynamic therapy (PDT) is frequently accompanied by induction of systemic immunosuppression. Photochemical mechanisms underlying this effect are not completely understood. Here, we demonstrate the immunosuppressive activity of photooxidation products of protoporphyrin IX dimethyl ester (PPIX) in a murine model of contact hypersensitivity (CHS) to 2,4-dinitrofluorobenzene (DNFB). Intravenous injection of the preirradiated solution of PPIX to mice resulted in fluence-dependent suppression of the CHS. The samples of photodecomposed PPIX with suppressive effect on the CHS contained chlorin-type products, namely, two isomers of photoprotoporphyrin (pPP1 and pPP2) as main photoproducts. Concentration-dependent suppression of the CHS was also induced when purified pPP1 or pPP2 were injected to mice intravenously. These purified photoproducts exerted equal immunosuppressive activity. The highest suppression of the CHS was induced when pPP1 was injected 20 h before sensitization with DNFB. The lowest suppression was at its injection time 24 h before challenge. The pPP1-induced suppression of the CHS was adoptively transferable and was associated with generation of cells with suppressive functions. These suppressor cells inhibited the efferent phase of the CHS. Our results strongly indicate that induction of systemic immunosuppression by PDT with PPIX may proceed through photobleaching of photosensitizer and generation of photoprotoporphyrins, which can affect T cell immunity.