RESUMO
Elucidating the nature of long-range intramolecular charge transport in π-conjugated molecules is of great importance for the development of organic electronic materials. However, the effects of the degree of π-conjugation on the hopping charge transport have not been experimentally explored so far owing to the lack of π-conjugated backbones with different conjugation degrees and several-nanometer lengths. Here we develop highly planar and completely insulated oligothiophenes between 0.85 and 9.64 nm in length. As compared to distorted oligothiophenes, single-molecule conductance measurements of the planar molecules show (i) a smaller activation energy and larger electrical conductance in the hopping transport regime and (ii) a shift in crossover between tunneling and hopping conduction toward a short molecular length. Theoretical calculations indicate that small reorganization energies and narrow energy gaps derived from the planar backbones result in these superior characteristics. This study reveals that the planarity of π-conjugation has significant advantages for hopping charge transport.
RESUMO
A series of oligothiophenes that incorporate cyclopenta[c]thiophene-based units bearing spiro-substituted dialkylfluorene was synthesized. Photophysical measurements indicated that there was no interruption in the conjugation along the oligothiophene backbones, irrespective of the number or position of this unit. Electrochemical measurements showed that the thiophene 7-mers and 11-mer exhibit reversible multi-oxidation waves. The formation of cationic species was clearly observed from UV/Vis/NIR measurements. Furthermore, the UV/Vis/NIR spectra at 223â K under one-electron oxidation conditions revealed that the unsubstituted thiophene or bithiophene units remained in the absence of intermolecular π-π interactions, whereas the formation of π-dimeric species was observed for the thiophene 7-mer containing an unsubstituted terthiophene (U3 ) unit. Theoretical calculations indicated that the combination of the U3 unit and the all-trans conformation decreased the intermolecular steric repulsion between the fused cyclopentene ring and its facing thiophene, which may contribute to the formation of the dimeric structure.
RESUMO
A cyclizative atmospheric CO(2) fixation by unsaturated amines such as allyl and propargyl amines under mild reaction conditions, efficiently leading to cyclic carbamates bearing a iodomethyl group, have been developed utilizing tert-butyl hypoiodite (t-BuOI).
RESUMO
In vitro treatment of thymocytes and splenocytes with rabbit complement (C') alone induced significant reductions in the proportion of NK-T cells in murine system. The reduction appeared to be prominent in the thymic NK-T cells compared to that in splenic NK-T cells. No reductions were detected in other populations, such as T, B and NK cells. Thus, NK-T cells lineage-specifically showed the enhanced C' sensitivity. However, NK-T cells in T cell receptor (TCR) transgenic mice of RAG-/- background that lack B cells and antibodies exhibited no C' sensitivity. On the other hand those from the same TCR transgenic mice of RAG intact background that have a normal population of B cells and antibodies showed the C' sensitivity similar to that in normal mice. These findings suggest that the enhanced C' sensitivity observed in the NK-T cell population is associated with the NK-T specific autoantibodies. Indeed, we found that a subset of NK-T cells in the thymus bound mouse immunoglobulins. Similar observations were obtained with several strains of lupus model mice, some of which show a decrease of NK-T cells with aging. Possible roles of the enhanced C' sensitivity of NK-T cells in pathophysiological conditions in various mouse strains including lupus models are discussed.