Kamrul Hasan

Tuning the Emission of Cationic Iridium (III) Complexes Towards the Red Through Methoxy Substitution of the Cyclometalating Ligand

The synthesis, characterization and evaluation in solid-state devices of a series of 8 cationic iridium complexes bearing different numbers of methoxy groups on the cyclometallating ligands are reported. The optoelectronic characterization showed a dramatic red shift in the absorption and the emission and a reduction of the electrochemical gap of the complexes when a methoxy group was introduced para to the Ir-C bond. The addition of a second or third methoxy group did not lead to a significant further red shift in these spectra. Emission maxima over the series ranged from 595 to 730 nm. All complexes possessing a motif with a methoxy group at the 3-position of the cyclometalating ligands showed very short emission lifetimes and poor photoluminescence quantum yields whereas complexes having a methoxy group at the 4-position were slightly blue shifted compared to the unsubstituted parent complexes, resulting from the inductively electron withdrawing nature of this directing group on the Ir-C bond. Light-emitting electrochemical cells were fabricated and evaluated. These deep red emitters generally showed poor performance with electroluminescence mirroring photoluminescence. DFT calculations accurately modelled the observed photophysical and electrochemical behavior of the complexes and point to an emission from a mixed charge transfer state.

Panchromic cationic iridium(III) complexes.

We report the synthesis, X-ray structures, and optoelectronic characterization of two cationic iridium complexes bearing bis[(4-methoxyphenyl)imino]acenaphthene ligands. These complexes exhibited panchromic absorption extending as far as 800 nm, making them of interest for solar-energy-harvesting applications.

Controlling the emission efficiency of blue-green iridium(III) phosphorescent emitters and applications in solution-processed organic light-emitting diodes

We show that the emission efficiency of blue-green phosphorescent emitters can be controlled through coupling of the excited state to vibrational modes. We controlled this vibrational coupling through choice of different ligands and as a result, complexes with CF3-groups on the ancillary ligand were essentially non-emissive (ΦPL 50%). Emission of the complexes can be drastically improved (30 times higher ΦPL compared to degassed solution for the CF3-containing complexes) by blending them with an inert solid host such as PMMA, which mitigates metal-ligand vibrations. Solution-processed organic light-emitting diodes made from these materials showed efficiency as high as 6.3%.

Localizing Facial Keypoints with Global Descriptor Search, Neighbour Alignment and Locally Linear Models

We present our technique for facial key point localization in the wild submitted to the 300-W challenge. Our approach begins with a nearest neighbour search using global descriptors. We then employ an alignment of local neighbours and dynamically fit a locally linear model to the global key point configurations of the returned neighbours. Neighbours are also used to define restricted areas of the input image in which we apply local discriminative classifiers. We then employ an energy function based minimization approach to combine local classifier predictions with the dynamically estimated joint key point configuration model. % Our method is able place 68 key points on in the wild facial imagery with an average localization error of less than 10% of the inter-ocular distance for almost 50% of the challenge test examples. Our model therein increased the yield of low error images over the baseline AAM result provided by the challenge organizers by a factor of 2.2 for the 68 key point challenge. Our method improves the 51 key point baseline result by a factor of 1.95, yielding key points for more than 50% of the test examples with error of less than 10% of inter-ocular distance.

Bay-Region Functionalisation of Ar-BIAN Ligands and Their Use Within Highly Absorptive Cationic Iridium(III) Dyes

We report the synthesis, UV-vis absorption, electrochemical characterisation, and DFT studies of five panchromatic, heteroleptic iridium complexes (four of which are new) supported by Ar-BIAN ligands. In particular, the synthesis of an ester-functionalised Ar-BIAN ligand was carried out by a mechanochemical milling approach, which was advantageous over conventional metal templating solution methods in terms of reaction time and product purity. The introduction of ester and carboxylate functionalities at the bay region of the acenaphthene motif increases each ligand’s π-accepting capacity and imparts grafting capabilities to the iridium complexes. These complexes have absorption profiles that surpass the renowned N3 dye [Ru(dcbpy)2(NCS)2] (dcbpy = 4,4′-dicarboxy-2,2′-bipyridine), making them of interest for solar-energy-harvesting applications.

Interaction of KRAS somatic mutation and colorectal carcinoma and its association with differential DNA methylation.

577 Background: We examined if KRAS somatic mutation in colorectal carcinoma (CRC) is associated with differential tumor DNA methylation. Methods: We did a genome-wide methylation assay (450K) for a total of 250 paired samples from 125 CRC patients (m = 72, f = 53) at different stages (stage 1: 25, stage II: 33 and stage III: 67). Of them 101 had left-sided CRC (descending colon to rectum); 30 had MSI, and 34 had somatic mutation in KRAS (rs112445441). Results: Frequency of KRAS mutation was not different between right and left-sided CRC (29% vs. 27%). But, like other series, MSI was more frequent in the right-sided tumor (54% vs. 17%, p = 0.003). In patients with wild type KRAS tumor (n = 91), paired comparison between tumor and corresponding normal tissue identified a total of 1244 tumor-specific differential methylation loci (DML) covering 532 genes that were significant at FDR 0.001 and magnitude of difference ≥ 20%; But similar analysis in patients with KRAS mutation (n = 34) revealed 7612 tumor-spec...