RESUMEN
In this work, we designed two nitrogen-bridged fluorene-based heptacyclic FNT and nonacyclic FNTT ladder-type structures, which were constructed by one-pot palladium-catalyzed Buchwald-Hartwig amination. FNT and FNTT were further end-capped by FIC acceptors to form two FNT-FIC and FNTT-FIC non-fullerene acceptors (NFAs), respectively. The two NFAs exhibit more red-shifted absorption and higher crystallinity compared to those of the corresponding carbon-bridged FCT-FIC and FCTT-FIC counterparts. Grazing incidence wide-angle X-ray scattering (GIWAXS) measurements reveal that the 2-butyloctyl groups on the nitrogen in the convex region of FNT-FIC interdigitate with the dioctyl groups on the fluorene in the concave region of another FNT-FIC, resulting in a lamellar packing structure with a d spacing of 13.27 Å. As a consequence, the PM6:FNT-FIC (1:1 wt %) device achieved a power conversion efficiency (PCE) of only 6.60%, primarily due to the highly crystalline nature of FNT-FIC, which induced significant phase separation between PM6 and FNT-FIC in the blended film. However, FNTT-FIC, featuring 2-butyloctyl groups positioned on the nitrogen within the concave region of its curved skeleton, exhibits improved donor-acceptor miscibility, thereby promoting a more favorable morphology. As a result, the PM6:FNTT-FIC (1:1.2 wt %) device exhibited a higher PCE of 12.15% with an exceptional Voc of 0.96 V. This research demonstrates that placing alkylamino moieties within the concave region of curved A-D-A NFAs leads to a better molecular design.
RESUMEN
The high-performance Y6-based nonfullerene acceptors (NFAs) feature a C-shaped A-DA'D-A-type molecular architecture with a central electron-deficient thiadiazole (Tz) A' unit. In this work, we designed and synthesized a new A-D-A-type NFA, termed CB16, having a C-shaped ortho-benzodipyrrole-based skeleton of Y6 but with the Tz unit eliminated. When processed with nonhalogenated xylene without using any additives, the binary PM6:CB16 devices display a remarkable power conversion efficiency (PCE) of 18.32% with a high open-circuit voltage (Voc) of 0.92 V, surpassing the performance of the corresponding Y6-based devices. In contrast, similarly synthesized SB16, featuring an S-shaped para-benzodipyrrole-based skeleton, yields a low PCE of 0.15% due to the strong side-chain aggregation of SB16. The C-shaped A-DNBND-A skeleton in CB16 and the Y6-series NFAs constitutes the essential structural foundation for achieving exceptional device performance. The central Tz moiety or other A' units can be employed to finely adjust intermolecular interactions. The single-crystal X-ray structure reveals that ortho-benzodipyrrole-embedded A-DNBND-A plays an important role in the formation of a 3D elliptical network packing for efficient charge transport. Solution structures of the PM6:NFAs detected by small- and wide-angle X-ray scattering (SWAXS) indicate that removing the Tz unit in the C-shaped skeleton could reduce the self-packing of CB16, thereby enhancing the complexing and networking with PM6 in the spin-coating solution and the subsequent device film. Elucidating the structure-property-performance relationships of A-DA'D-A-type NFAs in this work paves the way for the future development of structurally simplified A-D-A-type NFAs.
RESUMEN
BACKGROUND: Infiltrating macrophage count (IMC) is found to correlate with the progression and prognosis of many human cancers. METHODS: This study used immunohistochemistry to measure the IMC (macrophages/high-power field [HPF]) in 92 specimens of oral squamous cell carcinoma (OSCC). RESULTS: A significantly increased IMC was found in OSCCs with larger tumor size, positive lymph node metastasis, more advanced clinical stages, or recurrence (all ps < .05). Kaplan-Meier survival analysis found that OSCC patients with IMC >196 macrophages/HPF had a significantly shorter disease-free (p = .001, log-rank test) or overall survival (p < .001, log-rank test) than OSCC patients with IMC <196 macrophages/HPF. Multivariate Cox regression analyses showed that IMC >196 macrophages/HPF was an independent predictor for poor disease-free (p = .005) and overall survival of patients with OSCC (p = .015). CONCLUSIONS: The IMC can predict the progression and prognosis of OSCCs in Taiwan.
