Plexin domain-containing 1 may be a biomarker of poor prognosis in hepatocellular carcinoma patients, may mediate immune evasion.

BACKGROUND: For the first time, we investigated the oncological role of plexin domain-containing 1 (PLXDC1), also known as tumor endothelial marker 7 (TEM7), in hepatocellular carcinoma (HCC). AIM: To investigate the oncological profile of PLXDC1 in HCC. METHODS: Based on The Cancer Genome Atlas database, we analyzed the expression of PLXDC1 in HCC. Using immunohistochemistry, quantitative real-time polymerase chain reaction (qRT-PCR), and Western blotting, we validated our results. The prognostic value of PLXDC1 in HCC was analyzed by assessing its correlation with clinicopathological features, such as patient survival, methylation level, tumor immune microenvironment features, and immune cell surface checkpoint expression. Finally, to assess the immune evasion potential of PLXDC1 in HCC, we used the tumor immune dysfunction and exclusion (TIDE) website and immunohistochemical staining assays. RESULTS: Based on immunohistochemistry, qRT-PCR, and Western blot assays, overexpression of PLXDC1 in HCC was associated with poor prognosis. Univariate and multivariate Cox analyses indicated that PLXDC1 might be an independent prognostic factor. In HCC patients with high methylation levels, the prognosis was worse than in patients with low methylation levels. Pathway enrichment analysis of HCC tissues indicated that genes upregulated in the high-PLXDC1 subgroup were enriched in mesenchymal and immune activation signaling, and TIDE assessment showed that the risk of immune evasion was significantly higher in the high-PLXDC1 subgroup compared to the low-PLXDC1 subgroup. The high-risk group had a significantly lower immune evasion rate as well as a poor prognosis, and PLXDC1-related risk scores were also associated with a poor prognosis. CONCLUSION: As a result of this study analyzing PLXDC1 from multiple biological perspectives, it was revealed that it is a biomarker of poor prognosis for HCC patients, and that it plays a role in determining immune evasion status.

Photoluminescence and electroluminescence of iridium(iii) complexes with 2',6'-bis(trifluoromethyl)-2,4'-bipyridine and 1,3,4-oxadiazole/1,3,4-thiadiazole derivative ligands.

Using 2',6'-bis(trifluoromethyl)-2,4'-bipyridine as a monoanionic cyclometalated ligand, 2-(5-(4-(trifluoromethyl)phenyl)-1,3,4-oxadiazol-2-yl)phenol and 2-(5-(4-(trifluoromethyl) phenyl)-1,3,4-thiadiazol-2-yl)phenol as ancillary ligands, two new heteroleptic iridium(iii) complexes (Ir1 and Ir2) were prepared and investigated. The ancillary ligand variations affected their emissions greatly, and the complexes Ir1 and Ir2 emitted green (503 nm) and orange (579 nm) lights, respectively. Moreover, the electron mobility of the two complexes is as high as that of the electron transport material Alq3 (tris-(8-hydroxyquinoline)aluminium), which is useful for their performances in organic light-emitting diodes (OLEDs). The OLEDs with Ir1 as the emitter showed excellent performances with a maximum current efficiency of 74.8 cd A-1, a maximum external quantum efficiency of 27.0%, a maximum power efficiency of 33.4 lm W-1, and the efficiency roll-off is mild. These results suggest that complexes with 1,3,4-oxadiazole/1,3,4-thiadiazole derivatives have potential application as efficient emitters in OLEDs.

Novel Design of Iridium Phosphors with Pyridinylphosphinate Ligands for High-Efficiency Blue Organic Light-emitting Diodes.

Due to the high quantum efficiency and wide scope of emission colors, iridium (Ir) (III) complexes have been widely applied as guest materials for OLEDs (organic light-emitting diodes). Contrary to well-developed Ir(III)-based red and green phosphorescent complexes, the efficient blue emitters are rare reported. Like the development of the LED, the absence of efficient and stable blue materials hinders the widely practical application of the OLEDs. Inspired by this, we designed two novel ancillary ligands of phenyl(pyridin-2-yl)phosphinate (ppp) and dipyridinylphosphinate (dpp) for efficient blue phosphorescent iridium complexes (dfppy)2Ir(ppp) and (dfppy)2Ir(dpp) (dfppy = 2-(2,4-difluorophenyl)pyridine) with good electron transport property. The devices using the new iridium phosphors display excellent electroluminescence (EL) performances with a peak current efficiency of 58.78 cd/A, a maximum external quantum efficiency of 28.3%, a peak power efficiency of 52.74 lm/W and negligible efficiency roll-off ratios. The results demonstrated that iridium complexes with pyridinylphosphinate ligands are potential blue phosphorescent materials for OLEDs.

Syntheses, photoluminescence and electroluminescence of two novel platinum(ii) complexes.

Two new platinum(ii) cyclometalated complexes with 2-(4-trifluoromethyl)phenylpyridine (4-tfmppy) as the main ligand and tetraphenylimidodiphosphinate (tpip) (Pt-tpip) and tetra(4-fluorophenyl)imidodiphosphinate (ftpip) (Pt-ftpip) as ancillary ligands were developed. Both complexes were green phosphors with photoluminescence quantum efficiency yields of 71.5% and 79.2% in CH2Cl2 solution at room temperature, respectively. The organic light-emitting diodes with a double emissive layers structure of ITO/TAPC (1,1-bis(4-(di-p-tolylamino)phenyl)cyclohexane), 40 nm/Pt-tpip or Pt-ftpip: TcTa (4,4',4''-tri(9-carbazoyl)-triphenylamine) (5 wt%, 10 nm)/Pt-tpip or Pt-ftpip: 2,6DCzPPy (2,6-bis(3-(carbazol-9-yl)phenyl)pyridine) (5 wt%, 10 nm)/TmPyPB (1,3,5-tri(m-pyrid-3-yl-phenyl)benzene, 40 nm)/LiF (1 nm)/Al (100 nm) showed good performances. In particular, the device based on the Pt-ftpip complex with a 5 wt% doped concentration showed superior performance with a low drive voltage of 3.3 V, a maximum current efficiency of 48.3 cd A-1, a maximum external quantum efficiency of 14.0%, and a maximum power efficiency of 35.7 lm W-1, respectively. Even at a brightness of 1000 cd m-2, a current efficiency of 47.0 cd A-1 could still be obtained, suggesting that the ancillary ligands (tpip and ftpip) can be employed well in Pt(ii) complexes, which could find potential applications in OLEDs.

Circularly polarised phosphorescent photoluminescence and electroluminescence of iridium complexes.

Nearly all the neutral iridium complexes widely used as dopants in PhOLEDs are racemic mixtures; however, this study observed that these complexes can be separated into stable optically active Λ and ∆ isomers and that their chirality is an intrinsic property. The circularly polarised phosphorescent photoluminescence (CPPPL) signals of Λ/Δ isomers are perfect mirror images with opposite polarisation and equal intensity exhibiting a "handedness" for the polarisation. For the first time, we applied the Λ/Δ iridium isomers as emitters in OLEDs, and the circularly polarised phosphorescent electroluminescence (CPPEL) spectra reveal completely positive or negative broad peaks consistent with the CPPPL spectra. The results demonstrate that the Λ/Δ isomers have potential application for 3D OLEDs because they can exhibit high efficiency and luminance, and 3D display technology based on circularly polarised light is the most comfortable for the eyes.

Syntheses, photoluminescence, and electroluminescence of a series of iridium complexes with trifluoromethyl-substituted 2-phenylpyridine as the main ligands and tetraphenylimidodiphosphinate as the ancillary ligand.

Five bis-cyclometalated iridium complexes with tifluoromethyl-substituted 2-phenylpyridine (ppy) at different positions of its phenyl group as the main ligands and tetraphenylimidodiphosphinate (tpip) as the ancillary ligand, 2-6 (1 is a trifluoromethyl-free complex), were prepared, and their X-ray crystallography, photoluminescence, and electrochemistry were investigated. The number and positions of trifluoromethyl groups at the phenyl ring of ppy greatly affected the emission spectra of Ir(3+) complexes, and their corresponding emission peaks at 533, 502, 524, 480, and 542 nm were observed at room temperature, respectively. Constructed with complexes 2-6 as the emitters, respectively, the organic light-emitting diodes (OLEDs) with the structure of indium-tin oxide/1,1-bis[4-(di-p-tolylamino)phenyl]cyclohexane (30 nm)/Ir (x wt %):bis[3,5-bis(9H-carbazol-9-yl)phenyl]diphenylsilane (15 nm)/1,3,5-tris(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (45 nm)/LiF (1 nm)/Al (100 nm) showed good performances. Particularly, device G4 based on 4-trifluoromethyl-substituted complex 4 with x = 8 wt % obtained a maximum luminance of over 39000 cd m(-2) and maximum luminance efficiency (η(L)) and power efficiency (η(p)) of 50.8 cd A(-1) and 29.0 lm W(-1), respectively. The results suggested that all of the complexes 2-6 would have potential applications in OLEDs.

Synthesis and photoluminescence properties of rhenium(I) complexes based on 2,2':6',2''-terpyridine derivatives with hole-transporting units.

Based on 2,2':6',2''-terpyridine ligands (L1), five terpyridine derivatives, namely 4'-carbazol-9-yl-2,2':6',2''-terpyridine (L2), 4'-diphenylamino-2,2':6',2''-terpyridine (L3), 4'-bis(4-tert-butylphenyl)amino-2,2':6',2''-terpyridine (L4), 4'-[naphthalen-1-yl-(phenyl)amino]-2,2':6',2''-terpyridine (L5), 4'-[naphthalen-2-yl(phenyl)amino]-2,2':6',2''-terpyridine (L6) and their corresponding Re(I) complexes ReL(n)(CO)3Cl (n = 1­6) have been synthesized and characterized by elemental analysis and 1H NMR spectroscopy. The X-ray crystal structure of ReL3(CO)3Cl has also been obtained. The luminescence spectra of ReL2(CO)3Cl­ReL5(CO)3Cl, obtained in CH2Cl2 solution at room temperature, show strong dπ (Re) → π* (diimine) MLCT character (λ(max) 600 nm) and a small red shift relative to ReL1(CO)3Cl. This, confirmed by the study of the triplet energy levels of the L1­L6 ligands at low temperature (77 K rigid matrix), indicates that the introduction of electron-donating moieties on the terpyridine unit decreases the triplet levels of the ligands, leading to a reduction of the energy gap between d and π* orbitals. In the solid state, upon MLCT excitation, all the complexes show an even stronger emission and a blue spectral shift (λ(max) ∼ 550 nm) compared to those obtained in solution.