Effect of adoptive T-cell immunotherapy on immunological parameters and prognosis in patients with advanced pancreatic cancer

13301甲第5242号博士（医学）金沢大学博士論文本文Full 以下に掲載：Cytotherapy 23(2) pp.137-145 2021. Elsevier. 共著者：Tatsuo Kumai, Eishiro Mizukoshi, Tomomi Hashiba, Hidetoshi Nakagawa, Masaaki Kitahara, Tomoharu Miyashita, Takafumi Mochizuki, Shigenori Goto, Takashi Kamigaki, Rishu Takimoto, MD, Taro Yamashita, Yoshio Sakai, Tatsuya Yamashita, Masao Honda, Katsuro Tomita, Shuichi Kanek

Fundamenta Botanica Tom. VII

Here, we investigated photocarrier generation and diffusion characteristics in molecular-scale donor–acceptor charge-transfer (CT) systems. The photocarrier diffusion characteristics were measured on a series of mixed-stack CT compound crystals by the laser beam-induced current (LBIC) technique where the photocurrent is detected on the crystal surfaces as a function of either the laser illuminated position or the laser-modulation frequency. In the compounds with CT gap energy larger than 0.7 eV, the diffusion length of photocarriers reached larger than 10 μm. The dependence of diffusion length on the electric field and the laser-modulated frequency clearly indicates the direct generation of long-lived photocarriers without forming exciton. In contrast, the photocarrier diffusion was suppressed, and the diffusion length got smaller than 2 μm in the compounds with a gap energy smaller than 0.7 eV. We discuss that the electron–hole recombination becomes dominated when the CT gap energy is as small as the molecular reorganization energy. The results suggest that proper choice of donor–acceptor combination should promote efficient charge separation in organic photovoltaic cells (OPCs)

Highly stable and isomorphic donor–acceptor stacking in a family of n-type organic semiconductors of BTBT–TCNQ derivatives

Herein, we present the common structural features of a family of semiconducting molecular donor–acceptor (DA) compounds based on alkylated fused-ring thieno-acenes. Crystal structure analyses were conducted for 22 DA compounds of variously substituted benzothieno[3,2-b][1]benzothiophenes (BTBTs), unsubstituted dithieno[3,2-b:2’,3’-d]thiophene, and unsubstituted benzo[1,2-b:4,5-b’]dithiophene as donors, which were combined with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its fluorinated derivatives (FmTCNQ, m = 0, 1, 2, 4) as acceptors. Fourteen DA compounds of (substituted BTBT)(TCNQ derivative) formed isomorphous layered molecular packing, where the intermolecular stacking arrangements between the planar skeletons of BTBT and TCNQ were common to each other, and the various substituents played supplementary roles. Density functional theory calculations were conducted to investigate the intermolecular forces between π-electron cores along the DA stacks. Dispersion interactions were the dominant intermolecular attraction, showing weak stacking position dependence, while the short-range orbit–orbit interaction was always repulsive, irrespective of stacking. An important finding is that the orbit–orbit interaction has a relatively strong position dependence and leads to common structural features in the DA compounds. We discuss the origin of the isostructural nature of molecular DA compounds, which is crucial in searching for and exploring unique combinations of molecules with superior semiconducting characteristics

Enhanced Layered-Herringbone Packing due to Long Alkyl Chain Substitution in Solution-Processable Organic Semiconductors

Herein, we report the stabilization and modulation of <i>layered-herringbone</i> (LHB) packing, which is known to afford high-performance organic thin-film transistors, based on crystal structure analyses and calculations of intermolecular interaction energies for alkyl-substituted organic semiconductor (OSC) crystals. We systematically investigated the alkyl chain-length dependence of the crystal structures, solvent solubilities, and thermal characteristics for three series of symmetrically and asymmetrically alkyl-substituted benzothieno­[3,2-<i>b</i>]­[1]­benzothiophenes (BTBTs). All the series exhibit LHB packing when the BTBTs are substituted with relatively long alkyl chains (−C_<i>n</i>H_2<i>n</i>+1), i.e., <i>n</i> ≥ 4 for monoalkylated, <i>n</i> ≥ 6 for dialkylated, and <i>n</i> ≥ 5 for phenyl-alkylated BTBTs. LHB packing is also evident in the nonsubstituted and diethyl-substituted BTBTs, although those substituted with short alkyl chains generally did not feature LHB packing because of their lack of interchain ordering. The density functional theory calculations of the intermolecular interactions revealed that the BTBT cores inherently generate LHB packing, and the stability is increasingly enhanced by the alignment of longer alkyl chains. It was also found that the LHB packing is stabilized by keeping the size ratios of the total intermolecular attractive forces between the <i>T-shaped</i> and <i>slipped parallel</i> contacts at about 3:2 for all the LHB compounds, despite the slight structural modifications generated by the substituents. We discuss the effects of alkyl substitutions to modulate the LHB packing of the BTBT cores and thus the two-dimensional carrier transport in layered OSC crystals

Effects of Substituted Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor Crystals

Effects of Substituted Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor Crystal

Effects of Substituted Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor Crystals

Effects of Substituted Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor Crystal

Effects of Substituted Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor Crystals

Effects of Substituted Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor Crystal