Tien-Yau Luh

Bright-blue electroluminescence from a silyl-substituted ter-(phenylene–vinylene) derivative

A bright-blue electroluminescent device has been fabricated by using an emissive dopant and an electron-transporting host. The dopant was a highly photoluminescent silyl-substituted ter-(phenylene–vinylene) derivative [1,4-bis[4-(2-trimethylsilylvinly) styryl]-2,5-dibutoxybenzene (BTSB)]. BTSB was doped into a trimer of N-arylbenzimidazoles (TPBI) which functioned as the host and electron transporter. N,N′-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4-4′-diamine (NPB) was used as the hole transporter. The device, with a structure of indium tin oxide\NPB\TPBI:10%BTSB\TPBI\Mg:Ag, shows a bright blue emission of 11000 cd/m2 at a current density of 360 mA/cm2. The current efficiency of this device is about 3.2 cd/A at 20 mA/cm2.

DNA-damaging reagents induce apoptosis through reactive oxygen species-dependent Fas aggregation.

DNA-damaging reagents may kill tumor cells through the generation of reactive oxygen species (ROS). Cytotoxic reagents may also induce apoptosis of cancer cells in Fas–FADD-dependent manners. In this study, we explored the possible link between these two apparently distinct pathways in T leukemia cell Jurkat. Our results demonstrated that γ-irradiation, similar to cisplatin, induced apoptosis by triggering Fas aggregation and activating FADD-caspase-8 apoptotic cascade. The absence of caspase-8 or Fas greatly reduced the sensitivity to apoptosis mediated by DNA-damaging agents. In addition, apoptosis induced by cisplatin and γ-irradiation, but not by Fas, was inhibited by ROS scavengers, including N-acetyl cysteine, MnTBAP, and C60. Importantly, these ROS scavengers effectively prevented the clustering of Fas receptor induced by cisplatin and γ-irradiation. Our results suggest that cisplatin and γ-irradiation promote ROS production, which in turn contributes to Fas receptor aggregation and cell death. The novel coupling between ROS and Fas clustering likely plays a significant role in apoptosis triggered by DNA-damaging reagents in Fas-expressing leukemia cells.

Carboxyfullerene prevents iron-induced oxidative stress in rat brain

Abstract: Carboxyfullerene, a water‐soluble carboxylic acid derivative of a fullerene, was investigated as a protective agent against iron‐induced oxidative stress in the nigrostriatal dopaminergic system of anesthetized rats. Intranigral infusion of exclusive carboxyfullerene did not increase lipid peroxidation in substantia nigra or deplete dopamine content in striatum. Infusion of ferrous citrate (iron II) induced degeneration of the nigrostriatal dopaminergic system. An increase in lipid peroxidation in substantia nigra as well as decreases in K+‐evoked dopamine overflow and dopamine content in striatum were observed 7 days after the infusion. Co‐infusion of carboxyfullerene prevented iron‐induced oxidative injury. Furthermore, tyrosine hydroxylase‐immunoreactive staining showed that carboxyfullerene inhibited the iron‐induced loss of the dopaminergic nerve terminals in striatum. The antioxidative action of carboxyfullerene was verified by in vitro studies. Incubation of brain homogenates increased the formation of the Schiff base fluorescent products of malonaldehyde, an indicator of lipid peroxidation. Both autooxidation (without exogenous iron) and iron‐induced elevation of lipid peroxidation of brain homogenates were suppressed by carboxyfullerene in a dose‐dependent manner. Our results suggest that intranigral infusion of carboxyfullerene appears to be nontoxic to the nigrostriatal dopaminergic system. Furthermore, the potent antioxidative action of carboxyfullerene protects the nigrostriatal dopaminergic system from iron‐induced oxidative injury.

Inhibition of Group A Streptococcus Infection by Carboxyfullerene

ABSTRACT The effect of a water-soluble trimalonic acid derivative of fullerene, carboxyfullerene, against Streptococcus pyogenes infection was tested. Pretreatment with carboxyfullerene was able to protect mice from S. pyogenes infection in an air pouch model. S. pyogenes-induced death and skin injury were inhibited dose dependently by carboxyfullerene. Administration of carboxyfullerene via the peritoneum and air pouch at 3 h post-S. pyogenes infection was able to protect 33% of mice from death. Surveys of exudates of the air pouch of carboxyfullerene-treated mice revealed that survival of infiltrating neutrophils was prolonged and that the bacteria were eliminated as a result of enhanced bactericidal activity of the neutrophils. Furthermore, carboxyfullerene was able to directly inhibit in vitro growth of S. pyogenes. These data suggest that carboxyfullerene can be considered an antimicrobial agent for group A streptococcus infection.

Hole-transport properties of a furan-containing oligoaryl

We report the carrier transport properties of a furan-containing oligoaryl PF6, which contains no arylamine moiety in the molecular structure but exhibits competitive hole-transport capability in comparison with conventional arylamine-based hole-transport materials often used in organic light-emitting devices (OLEDs) and xerography. Thin films of this compound exhibit both morphological stability and appropriate energy levels for OLED applications. OLEDs using PF6 as the hole-transport layer show low turn-on voltage, high efficiency, and high brightness competitive with those using conventional hole-transport materials, strongly indicating superior hole-transport properties of PF6. The carrier mobility of PF6 was directly measured by the time-of-flight transient photocurrent technique under various temperatures and electric fields. Nondispersive hole transport was observed and a room-temperature hole mobility in excess of 10−3 cm2/V s was obtained under high fields. The field and temperature dependence of...

Non-amine-based furan-containing oligoaryls as efficient hole transporting materialsElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b2/b207489c/

A new class of highly stable furan-based hole transporting oligomeric materials, synthesized from the corresponding propargylic dithioacetals, serve as efficient hole transporting materials in electroluminescent devices. The performance of the devices using these furan materials is comparable with or somewhat better than those employing the conventional triarylamines (e.g. alpha-NPD).

Ladderphanes: a new type of duplex polymers.

A polymeric ladderphane is a step-like structure comprising multiple layers of linkers covalently connected to two or more polymeric backbones. The linkers can be planar aromatic, macrocyclic metal complexes, or three-dimensional organic or organometallic moieties. Structurally, a DNA molecule is a special kind of ladderphane, where the cofacially aligned base-pair pendants are linked through hydrogen bonding. A greater understanding of this class of molecules could help researchers develop new synthetic molecules capable of a similar transfer of chemical information. In this Account, we summarize our studies of the strategy, design, synthesis, characterization, replications, chemical and photophysical properties, and assembly of a range of double-stranded ladderphanes with many fascinating structures. We employed two norbornene moieties fused with N-arylpyrrolidine to connect covalently with a range of relatively rigid linkers. Ring opening metathesis polymerizations (ROMP) of these bis-norbornenes using the first-generation Grubbs ruthenium-benzylidene catalyst produced the corresponding symmetrical double-stranded ladderphanes. The N-arylpyrrolidene moiety in the linker controls the isotactic selectivity and the trans configuration for all double bonds in both single- and double-stranded polynorbornenes. The π-π interactions between these aryl pendants may contribute to the high stereoselectivity in the ROMP of these substrates. We synthesized chiral helical ladderphanes by incorporating asymmetric center(s) in the linkers. Replication protocols and sequential polymerization of a monomer that includes two different polymerizable groups offer methods for producing unsymmetical ladderphanes. These routes furnish template synthesis of daughter polymers with well-controlled chain lengths and polydispersities. The linkers in these ladderphanes are well aligned in the center along the longitudinal axis of the polymer. Fluorescence quenching, excimer formation, or Soret band splitting experiments suggest that strong interactions take place between the linkers. The antiferromagnetism of the oxidized ferrocene-based ladderphanes further indicates strong coupling between linkers in these ladderphanes. These polynorbornene-based ladderphanes can easily aggregate to form a two-dimensional, highly ordered array on the graphite surface with areas that can reach the submicrometer range. These morphological patterns result from interactions between vinyl and styryl end groups via π-π stacking along the longitudinal axis of the polymer and van der Waals interaction between backbones of polymers. Such assembly orients planar arene moieties cofacially, and polynorbornene backbones insulate each linear array of arenes from the adjacent arrays. Dihydroxylation converts the double bonds in polynorbornene backbones of ladderphanes into more hydrophilic polyols. Hydrogen bonding between these polyol molecules leads to self-assembly and produces structures with longitudinally staggered morphologies on the graphite surface.

Alternating divinylarene–silylene copolymers

A summary of recent advances on the chemistry and photophysics of silylene-spaced divinylarene copolymers is presented. The silicon moieties have been shown to serve as an insulating spacer in these copolymers. The photophysical studies have provided useful insights into how chromophores in polymers interact intramolecularly. Because different chromophores can be regioregularly introduced into the polymeric chain, these copolymers have been extensively used as models for studying energy transfer, light harvesting as well as chiroptical transfer.

Oligomeric Tectonics: Supramolecular Assembly of Double‐Stranded Oligobisnorbornene through π–π Stacking

Self-assembly at the molecular level in solutions or on a surface is a subject of current interest. Herein we describe the tailoring of oligobisnorbornene 1, which represents an innovative concept of a preorganized building block on the tens of nanometer scale. The rodlike 1 has vinyl and styrenyl end groups. Scanning tunneling microscopy (STM) reveals that the oligomers aggregate anisotropically along the long axis and form a one-dimensional assembly in which, remarkably, no interstitial gap appears between neighboring oligomers. Dynamic light-scattering (DLS) measurements indicate that the assembly develops in solution. With a shear treatment for dropcast films, a unidirectionally ordered domain with a defect density less than 0.5 % can be prepared. Simulation results by molecular dynamics suggest that there may be multiple interactions such as pi-pi stacking and dipolar attractions taking place between the termini of the oligomers. To demonstrate the importance of double bonds in the oligomeric backbones and termini towards the tectonic assembly, a hydrogenated analogue was synthesized; pi-pi interactions are thus less significant and the film morphology is completely different from that of 1. This work extends the concept of molecular tectonics to preorganized oligomers and opens up a new avenue of nanopatterning toward nanodevices.

Fuzzy-junction organic light-emitting devices

A “fuzzy-junction” organic light-emitting device (OLED) containing a graded organic–organic interface is reported. Such graded junction is effectively produced utilizing interdiffusion through an ultrathin interfacial fusing layer sandwiched between two functional layers. With a glass transition temperature (Tg) lower than remaining layers, this fusing layer permits smooth interdiffusion and mixing of neighboring layers by annealing above its Tg. With appropriate material combinations, fuzzy-junction OLEDs thus prepared exhibit both reduced voltage and enhanced emission efficiency in comparison with conventional abrupt-junction devices. As an instance, a green fluorescent OLED with such fuzzy junction shows a high peak power efficiency of ∼20 lm/W, substantially higher than ∼14 lm/W of a corresponding abrupt-junction device.