New semi-ladder polymers for ambipolar organic light-emitting transistors.

Organic light-emitting transistors (OLETs) combine the light-emitting and gate-modulated electrical switching functions in a single device. Over the past two decades, progress has been made in developing new fluorescent semiconductors and device engineering to improve the properties of OLETs. In this paper, we give a brief review of the achievement and disadvantages of the present polymer-based OLETs, while highlighting the recent developments in semi-ladder polymers from our lab for new electroluminescent materials. The special folded molecular structures and unique aggregation states make these polymers suitable for exploration as OLET materials. A short conclusion is provided with a discussion on the challenges and future perspectives in this field.

Protective Effects of Necrostatin-1 in Acute Pancreatitis: Partial Involvement of Receptor Interacting Protein Kinase 1.

Acute pancreatitis (AP) is a severe and potentially fatal disease caused predominantly by alcohol excess and gallstones, which lacks a specific therapy. The role of Receptor-Interacting Protein Kinase 1 (RIPK1), a key component of programmed necrosis (Necroptosis), is unclear in AP. We assessed the effects of RIPK1 inhibitor Necrostatin-1 (Nec-1) and RIPK1 modification (RIPK1K45A: kinase dead) in bile acid (TLCS-AP), alcoholic (FAEE-AP) and caerulein hyperstimulation (CER-AP) mouse models. Involvement of collateral Nec-1 target indoleamine 2,3-dioxygenase (IDO) was probed with the inhibitor Epacadostat (EPA). Effects of Nec-1 and RIPK1K45A were also compared on pancreatic acinar cell (PAC) fate in vitro and underlying mechanisms explored. Nec-1 markedly ameliorated histological and biochemical changes in all models. However, these were only partially reduced or unchanged in RIPK1K45A mice. Inhibition of IDO with EPA was protective in TLCS-AP. Both Nec-1 and RIPK1K45A modification inhibited TLCS- and FAEE-induced PAC necrosis in vitro. Nec-1 did not affect TLCS-induced Ca2+ entry in PACs, however, it inhibited an associated ROS elevation. The results demonstrate protective actions of Nec-1 in multiple models. However, RIPK1-dependent necroptosis only partially contributed to beneficial effects, and actions on targets such as IDO are likely to be important.

Synergy between Photoluminescence and Charge Transport Achieved by Finely Tuning Polymeric Backbones for Efficient Light-Emitting Transistor.

The lack of design principle for developing high-performance polymer materials displaying strong fluorescence and high ambipolar charge mobilities limited their performance in organic light-emitting transistors (OLETs), electrically pumped organic laser, and other advanced electronic devices. A series of semiladder polymers by copolymerization of weak acceptors (TPTQ or TPTI) and weak donors (fluorene (F) or carbazole (C)) have been developed for luminescent and charge transporting properties. It was found that enhanced planarity, high crystallinity, and a delicate balance in interchain aggregation obtained in the new copolymer, TPTQ-F, contributed to high ambipolar charge mobilities and photoluminescent quantum yield. TPTQ-F showed excellent performance in solution-processed multilayered OLET devices with an external quantum efficiency (EQE) of 5.3%.

Finely Designed P3HT-Based Fully Conjugated Graft Polymer: Optical Measurements, Morphology, and the Faraday Effect.

In this work, our group synthesized and characterized a fully conjugated graft polymer comprising of a donor-acceptor molecular backbone and regioregular poly(3-hexylthiophene) (RRP3HT) side chains. Here, our macromonomer (MM) was synthesized via Kumada catalyst transfer polycondensation reaction based on ditin-benzodithiophene (BDT) initiator. The tin content of MM was then investigated by inductively coupled plasma-mass spectrometry (ICP-MS), which allowed for accurate control of donor/acceptor monomer ratio of 1:1 for the following Stille coupling polymerization toward our graft polymer (BP). The structures of the polymers were then characterized by gel permeation chromatography (GPC), NMR, and elemental analysis. This was followed by the characterization of optical, electrochemical, and physical properties. The magneto-optical activity of graft polymer BP was then measured. It was found that, despite the presence of the acceptor backbone, the characteristic large Faraday rotation of RRP3HT was maintained in polymer BP, which exhibited a Verdet constant of 2.39 ± 0.57 (104) °/T·m.

Foldable semi-ladder polymers: novel aggregation behavior and high-performance solution-processed organic light-emitting transistors.

A critical issue in developing high-performance organic light-emitting transistors (OLETs) is to balance the trade-off between charge transport and light emission in a semiconducting material. Although traditional materials for organic light-emitting diodes (OLEDs) or organic field-effect transistors (OFETs) have shown modest performance in OLET devices, design strategies towards high-performance OLET materials and the crucial structure-performance relationship remain unclear. Our research effort in developing cross-conjugated weak acceptor-weak donor copolymers for luminescent properties lead us to an unintentional discovery that these copolymers form coiled foldamers with intramolecular H-aggregation, leading to their exceptional OLET properties. An impressive external quantum efficiency (EQE) of 6.9% in solution-processed multi-layer OLET devices was achieved.

Molecular Design towards Controlling Charge Transport.

Organic electronics generally deals with bulk, statistically averaged electrical properties of organic materials. Single-molecule electronic devices can then be viewed as linkers to these bulk properties. However, controlling charge transport in single-molecule systems still remains a formidable task and has prevented proliferation of these systems from research laboratories to household electronics. This Concept article provides a general overview of the recent advances made by our group in the field. We will describe several concepts in designing molecular functions towards controlling charge transport through molecular systems. It should be noted, however, that this Concept article is by no means comprehensive and readers should look elsewhere for a more comprehensive picture of molecular electronics.

Enhancement in Open-Circuit Voltage in Organic Solar Cells by Using Ladder-Type Nonfullerene Acceptors.

The open-circuit voltage ( Voc) loss has always been a major factor in lowering power conversion efficiencies (PCEs) in bulk heterojunction organic photovoltaic cells (OPVs). A method to improve the Voc is indispensable to achieve high PCEs. In this paper, we investigated a series of perylene diimide-based ladder-type molecules as electron acceptors in nonfullerene OPVs. The D-A ladder-type structures described here lock our π-systems into a planar structure and eliminate bond twisting associated with linear conjugated systems. This enlarges the interface energy gap (Δ EDA), extends electronic delocalization, and hence improves the Voc. More importantly, these devices showed an increase in Voc without compromising either the Jsc or the FF. C5r exhibited a strong intermolecular interaction and a PCE value of 6.1%. Moreover, grazing-incident wide-angle X-ray scattering analysis and atomic force microscopy images suggested that our fused-ring acceptors showed a suitable domain size and uniform blend films, which were not affected by their rigid molecular structures.

Synthesis of Alternating Donor-Acceptor Ladder-Type Molecules and Investigation of Their Multiple Charge-Transfer Pathways.

We describe the synthesis as well as the optical and charge-transport properties of a series of donor-acceptor (D-A) ladder-type heteroacenes. These molecules are stable, soluble, and contain up to 24 fused rings. Structural analyses indicated that the backbones of S 10r and Se 10r are bent in single crystals. The three 10-ring heteroacenes were functionalized with thiol anchoring groups and used for single-molecular conductance measurements. The highest conductance was observed for molecular wires containing a benzoselenadiazole (BSD) moiety, which exhibits the narrowest band gap. Multiple charge-transport pathways were observed in molecular wires containing either benzothiadiazole (BTD) or BSD. The conductance is a complex function of both energy gap and orbital alignment.

Ovarian masses: is multi-detector computed tomography a reliable imaging modality?

BACKGROUND: Ovarian cancer continues to pose a major challenge to physicians and radiologists. It is the third most common gynecologic malignancy and estimated to be fifth leading cancer cause of death in women, constituting 23% of all gynecological malignancies. Multi-detector computed tomography (MDCT) appears to offer an excellent modality in diagnosing ovarian cancer based on combination of its availability, meticulous technique, efficacy and familiarity of radiologists and physicians. The aim of this study was to compute sensitivity, specificity, positive and negative predictive values and diagnostic accuracy of 64- slice MDCT in classifying ovarian masses; 95% confidence intervals were reported. MATERIALS AND METHODS: We prospectively designed a cross-sectional analytical study to collect data from July 2010 to August 2011 from a tertiary care hospital in Karachi, Pakistan. A sample of 105 women aged between 15-80 years referred for 64-MDCT of abdomen and pelvis with clinical suspicion of malignant ovarian cancer, irrespective of stage of disease, were enrolled by non- probability purposive sampling. All patients who were already known cases of histologically proven ovarian carcinoma and having some contraindication to radiation or iodinated contrast media were excluded. RESULTS: Our prospective study reports sensitivity, specificity; positive and negative predictive values with 95%CI and accuracy were computed. Kappa was calculated to report agreement among the two radiologists. For reader A, MDCT was found to have 92% (0.83, 0.97) sensitivity and 86.7% (0.68, 0.96) specificity, while PPV and NPV were 94.5% (0.86, 0.98) and 86.7% (0.63, 0.92), respectively. Accuracy reported by reader A was 90.5%. For reader B, sensitivity, specificity, PPV and NPV were 94.6% (0.86, 0.98) 90% (0.72, 0.97) 96% (0.88, 0.99) and 87.1% (0.69, 0.95) respectively. Accuracy computed by reader B was 93.3%. Excellent agreement was found between the two radiologists with a significant kappa value of 0.887. CONCLUSION: Based on our study results, we conclude MDCT is a reliable imaging modality in diagnosis of ovarian masses accurately with insignificant interobserver variability.