Anisotropy of Charge Transport in a Uniaxially Aligned and Chain‐Extended,High‐Mobility,Conjugated Polymer Semiconductor

Charge transport in the ribbon phase of poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT)—one of the most highly ordered, chain‐extended crystalline microstructures available in a conjugated polymer semiconductor—is studied. Ribbon‐phase PBTTT has previously been found not to exhibit high carrier mobilities, but it is shown here that field‐effect mobilities depend strongly on the device architecture and active interface. When devices are constructed such that the ribbon‐phase films are in contact with either a polymer gate dielectric or an SiO₂ gate dielectric modified by a hydrophobic, self‐assembled monolayer, high mobilities of up to 0.4 cm² V^?1 s^?1 can be achieved, which is comparable to those observed previously in terrace‐phase PBTTT. In uniaxially aligned, zone‐cast films of ribbon‐phase PBTTT the mobility anisotropy is measured for transport both parallel and perpendicular to the polymer chain direction. The mobility anisotropy is relatively small, with the mobility along the polymer chain direction being higher by a factor of 3–5, consistent with the grain size encountered in the two transport directions.     

Role of the Anion on the Transport and Structure of Organic Mixed Conductors

Organic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium‐ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte‐mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.     

The Effect of Alkyl Spacers on the Mixed Ionic-Electronic Conduction Properties of N-Type Polymers

Conjugated polymers with mixed ionic and electronic transport are essential for developing the complexity and function of electrochemical devices. Current n-type materials have a narrow scope and low performance compared with their p-type counterparts, requiring new molecular design strategies. This work presents two naphthalene diimide-bithiophene (NDI-T2) copolymers functionalized with hybrid alkyl-glycol side chains, where the naphthalene diimide unit is segregated from the ethylene glycol (EG) units within the side chain by an alkyl spacer. Introduction of hydrophobic propyl and hexyl spacers is investigated as a strategy to minimize detrimental swelling close to the conjugated backbone and balance the mixed conduction properties of n-type materials in aqueous electrolytes. It is found that both polymers functionalized with alkyl spacers outperform their analogue bearing EG-only side chains in organic electrochemical transistors (OECTs). The presence of the alkyl spacers also leads to remarkable stability in OECTs, with no decrease in the ON current after 2 h of operation. Through this versatile side chain modification, this work provides a greater understanding of the structure-property relationships required for n-type OECT materials operating in aqueous media.     

Bimolecular Crystals of Fullerenes in Conjugated Polymers and the Implications of Molecular Mixing for Solar Cells

The performance of polymer:fullerene bulk heterojunction solar cells is heavily influenced by the interpenetrating nanostructure formed by the two semiconductors because the size of the phases, the nature of the interface, and molecular packing affect exciton dissociation, recombination, and charge transport. Here, X‐ray diffraction is used to demonstrate the formation of stable, well‐ordered bimolecular crystals of fullerene intercalated between the side‐chains of the semiconducting polymer poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene. It is shown that fullerene intercalation is general and is likely to occur in blends with both amorphous and semicrystalline polymers when there is enough free volume between the side‐chains to accommodate the fullerene molecule. These findings offer explanations for why luminescence is completely quenched in crystals much larger than exciton diffusion lengths, how the hole mobility of poly(2‐methoxy‐5‐(3′,7′‐dimethyloxy)‐p‐phylene vinylene) increases by over 2 orders of magnitude when blended with fullerene derivatives, and why large‐scale phase separation occurs in some polymer:fullerene blend ratios while thermodynamically stable mixing on the molecular scale occurs for others. Furthermore, it is shown that intercalation of fullerenes between side chains mostly determines the optimum polymer:fullerene blending ratios. These discoveries suggest a method of intentionally designing bimolecular crystals and tuning their properties to create novel materials for photovoltaic and other applications.     

Computational Methods for Cardiac Electromechanics

Computational modeling provides a potentially powerful way to integrate structural properties measured in vitro to physiological functions measured in vivo. Focusing on the various scales (cell-tissue-organ-system), we give an overview of the importance and applications of numerical models of ventricular anatomy, electrophysiology, mechanics, and circulatory models. The integration of these models in one multiscale model of cardiac electromechanics is discussed in the light of applications to hypothesis generation, diagnosis, surgery(planning, training, and outcome of interventions), and therapies. Special attention is paid to practical use in terms of computational demand. Because of growing computer power and the development of efficient algorithms, we expect that real-time simulations with multiscale models of cardiac electromechanics become feasible in 2008 (despite the increasing complexity of models due to data accumulation on molecular and cellular mechanisms).     

On the Role of Contact Resistance and Electrode Modification in Organic Electrochemical Transistors

Contact resistance is renowned for its unfavorable impact on transistor performance. Despite its notoriety, the nature of contact resistance in organic electrochemical transistors (OECTs) remains unclear. Here, by investigating the role of contact resistance in n‐type OECTs, the first demonstration of source/drain‐electrode surface modification for achieving state‐of‐the‐art n‐type OECTs is reported. Specifically, thiol‐based self‐assembled monolayers (SAMs), 4‐methylbenzenethiol (MBT) and pentafluorobenzenethiol (PFBT), are used to investigate contact resistance in n‐type accumulation‐mode OECTs made from the hydrophilic copolymer P‐90, where the deliberate functionalization of the gold source/drain electrodes decreases and increases the energetic mismatch at the electrode/semiconductor interface, respectively. Although MBT treatment is found to increase the transconductance three‐fold, contact resistance is not found to be the dominant factor governing OECT performance. Additional morphology and surface energy investigations show that increased performance comes from SAM‐enhanced source/drain electrode surface energy, which improves wetting, semiconductor/metal interface quality, and semiconductor morphology at the electrode and channel. Overall, contact resistance in n‐type OECTs is investigated, whilst identifying source/drain electrode treatment as a useful device engineering strategy for achieving state of the art n‐type OECTs.     

Proximal median and ulnar resections. Results of primary and secondary repairs

PURPOSE OF THE STUDY: Recovery after median and ulnar nerve proximal repair is widely appreciated. The place and time for secondary functional reconstruction remains controversial. MATERIAL AND METHOD: From January 1983 to January 1990, 66 patients suffering from proximal injury of the median or ulnar nerves underwent nerve repair. Forty-five patients had a postoperative follow-up of more than 24 months: 24 isolated ulnar nerve lesions, 12 isolated median nerve lesions, and 9 combined median and ulnar nerve lesions. Ten patients were given a primary microsurgical nerve suture in our department. Thirty-eight patients underwent a delayed or secondary nerve repair of one or both nerves: 8 secondary nerve sutures, and 35 nerve grafts in 31 patients. RESULTS: Muscular strength, sensitivity, motion, and pain were better after primary nerve sutures (when technically possible) or after shortly delayed secondary sutures, although 40 per cent of patients treated with nerve grafts get final "good" or "very good" results. The time between the injury and nerve repair was the most significant prognosis factor. Results of ulnar nerve repairs at the elbow were statistically better with anterior transposition as compared to in situ repairs (p < 0.005). Fourteen patients required secondary functional reconstruction. Tendon transfers were performed at least 24 months after nerve repair. DISCUSSION: Nerve repair of proximal lesion to the median or ulnar nerves depends on the type of injury, but is advised even when delayed. Residual deficit following nerve repair should require functional transfers depending on hand sensitivity and extrinsic function.     

Selective spatial memory impairment after right unilateral temporal lobectomy

Deficits in performance of both spatial and visual tasks are common following tissue loss in the right temporal lobe. Since spatial and visual attributes are frequently confounded in experimental tasks, we have studied patients following unilateral temporal lobectomy, in an attempt to determine which aspect mediates the observed deficits. Spatial and visual memory performance was compared in normal controls (n = 16), left temporal (LTL; n = 19) and right temporal (RTL; n = 19) lobectomy patients, by presentation of eight abstract designs in a spatial array for subsequent recall and recognition of the designs (visual memory) and recall of their spatial position (spatial memory). By varying the retention intervals for each group, all three groups were matched on both recall and recognition of the designs at sub-ceiling levels. In contrast, recall of the position of the designs (spatial memory), tested at equivalent delays to those of the visual memory tests, revealed a deficit in the RTL patients compared to both controls and LTL patients (p < 0.05). Magnetic resonance imaging (MRI) was used to quantify the extent of resection of the hippocampus and parahippocampal regions in the two patient groups and showed a significant correlation between hippocampal and parahippocampal removal and spatial memory in the RTL group only. These data support the notion of a disproportionately large involvement of the right hippocampus and adjacent regions in spatial memory.     

Peritubular transport of ochratoxin A in rabbit renal proximal tubules

The transport of the nephrotoxic mycotoxin ochratoxin A across the renal peritubular membrane was examined in suspensions of rabbit renal proximal tubules. Ochratoxin A transport across the peritubular membrane was a high-affinity, low-capacity carrier-mediated process with a Jmax value of 0.12 +/- 0.4 nmol/mg of protein/min and a Km value of 1.4 +/- 0.1 microM. The apparent Michaelis constants for inhibition of [3H]para-aminohippurate (PAH) uptake by ochratoxin A inhibition was 1.5 microM, which is similar to the Km value for ochratoxin A uptake in tubule suspensions and suggests that ochratoxin A could be a substrate for the organic anion pathway. The capacity and affinity for peritubular ochratoxin A transport were 40-fold lower and > 100-fold greater, respectively, than those measured for the peritubular uptake of [3H]PAH in tubule suspensions. A concentration of 2.5 mM PAH, which reduced the uptake of [3H]PAH by 90%, reduced ochratoxin A uptake by only 40% to 50%, whereas probenecid concentrations of 0.6 to 2 mM reduced ochratoxin A accumulation in tubule suspensions up to approximately 80% to 90%. This probenecid-sensitive, PAH-insensitive uptake of ochratoxin A suggested that at least one mediated pathway other than the organic anion transporter was involved in the peritubular uptake of this mycotoxin. A 2 mM concentration of the fatty acid octanoate and 1.5 mM concentration of the nonsteroidal anti-inflammatory agent piroxicam were as effective as probenecid in blocking ochratoxin A uptake. The apparent Ki values for inhibition of ochratoxin A uptake by probenecid, piroxicam and octanoate were 30.5 +/- 7.9, 23.2 +/- 10.4 and 81.5 +/- 8.7 microM, respectively. The ability of octanoic acid to inhibit ochratoxin A transport to the same extent as probenecid and a greater extent than PAH suggests that a separate fatty acid transport pathway may be involved in the accumulation of ochratoxin A by suspensions of rabbit renal proximal tubules.     

Differential effect of steady versus oscillating flow on bone cells

Loading induced fluid flow has recently been proposed as an important biophysical signal in bone mechanotransduction. Fluid flow resulting from activities which load the skeleton such as standing, locomotion, or postural muscle activity are predicted to be dynamic in nature and include a relatively small static component. However, in vitro fluid flow experiments with bone cells to date have been conducted using steady or pulsing flow profiles only. In this study we exposed osteoblast-like hFOB 1.19 cells (immortalized human fetal osteoblasts) to precisely controlled dynamic fluid flow profiles of saline supplemented with 2% fetal bovine serum while monitoring intracellular calcium concentration with the fluorescent dye fura-2. Applied flows included steady flow resulting in a wall shear stress of 2 N m(-2), oscillating flow (+/-2 Nm(-2)), and pulsing flow (0 to 2 N m(-2)). The dynamic flows were applied with sinusoidal profiles of 0.5, 1.0, and 2.0 Hz. We found that oscillating flow was a much less potent stimulator of bone cells than either steady or pulsing flow. Furthermore, a decrease in responsiveness with increasing frequency was observed for the dynamic flows. In both cases a reduction in responsiveness coincides with a reduction in the net fluid transport of the flow profile. Thus. these findings support the hypothesis that the response of bone cells to fluid flow is dependent on chemotransport effects.