Helical growth of semiconducting columnar dye assemblies based on chiral perylene bisimides.

A perylene bisimide derivative bearing two phenyl substituents with chiral solubilizing alkyl chains at the imide N atoms has been synthesized, and its self-assembly properties in solution and condensed phase have been investigated. Temperature-dependent CD spectra revealed the coexistence of two different kinds of chiral aggregates, differing in size and handedness. The chiral side chains effect a higher order within the self-assemblies, resulting in an increased charge-carrier mobility in the columnar liquid crystalline mesophase. [structure: see text]

Efficient charge transport along phenylene-vinylene molecular wires.

We have studied the motion of charge carriers along isolated phenylene-vinylene (PV) chains using a combination of experimental and theoretical methods. The conductive properties of positive charges along PV chains in dilute solution were studied by using the pulse-radiolysis time-resolved microwave conductivity (TRMC) technique. This technique enables the measurement of high-frequency (tens of GHz) charge carrier mobilities along isolated PV chains without the use of electrodes. The charge carrier mobility along PV chains with finite and infinite length was studied theoretically by charge transport simulations with parameters from density functional theory (DFT) calculations. The high-frequency charge carrier mobility is found to depend strongly on the conjugation length of the PV chains and is found to increase both with increasing length of the PV chain and with increasing conjugation fraction. The experimental results are in good agreement with the calculated results. On the basis of this combined experimental and theoretical study an intrachain charge carrier mobility of a few tens of cm2/Vs is expected for an infinitely long PV chain without conjugation breaks.

Functional organogels from highly efficient organogelator based on perylene bisimide semiconductor.

A new n-type semiconducting perylene bisimide dye has been synthesized that gelates a broad variety of organic solvents to afford well-defined nano- and mesoscopic helical fibers and bundles.

Characteristics and performance of the first commercial multileaf collimator for a robotic radiosurgery system.

PURPOSE: The "InCise™ multileaf-collimator (MLC)" is the first commercial MLC to be mounted on a robotic SRS/SBRT platform (CyberKnife). The authors assessed characteristics and performance of this novel device in a preclinical five months test period. METHODS: Commissioning beam data were acquired with unshielded diodes. EBT3 radiochromic films were employed for measurement of transmission, leaf/bank position accuracy (garden fence) before and after exercising the MLC, for end-to-end testing and further characterization of the beam. The robot workspace with MLC was assessed analytically by transformation to an Euler geometry ("plane," "gantry," and "collimator" angles) and by measuring pointing accuracy at each node. Stability over time was evaluated in picket fence and adapted Winston-Lutz tests (AQA). RESULTS: Beam penumbrae (80%-20%, with 100% = 2 × dose at inflection point for field sizes ≥ 50 × 50 mm(2)) were 2.2-3.7 mm for square fields in reference condition (source-axis-distance 800 mm, depth 15 mm) and depended on field size and off-axis position. Transmission and leakage did not exceed 0.5%. Accessible clinical workspace with MLC covered non-coplanar gantry angles of [-113°; +112°] and collimator angles of [-100°; +107°], with an average robot pointing accuracy of 0.12 ± 0.09 mm. For vertical beams, garden fence tests exhibited an average leaf positioning error of ≤0.2 mm, which increased by 0.25 and 0.30 mm (banks X1 and X2) with leaves traveling parallel to gravity. After execution of a leaf motion stress routine, garden fence tests showed slightly increased jaggedness and allowed to identify one malfunctioning leaf motor. Total system accuracy with MLC was 0.38 ± 0.05 mm in nine end-to-end tests. Picket fence and AQA tests displayed stable results over the test period. CONCLUSIONS: The InCise™ MLC for CyberKnife showed high accuracy and adequate characteristics for SRS/SBRT applications. MLC performance after exercise demands specific quality assurance measures.

A fluorine-substituted hexakisdecyloxy- hexa-peri-hexabenzocoronene.

[structure: see text] The first fluorine-substituted hexabenzocoronene has been synthesized and is much more readily reduced than its nonfluorinated analogues. Thin films of this material show columnar order at room temperature, and the charge-carrier mobility measured by the pulse-radiolysis time-resolved microwave conductivity technique is comparable to that of other hexabenzocoronene materials.

Charge transport in self-organized pi-stacks of p-phenylene vinylene oligomers.

We have studied the mobility of charge carriers along self-organizing pi-stacks of hydrogen-bonded phenylene vinylene oligomers in solution, by time-resolved microwave conductivity measurements. The value deduced for the mobility along the stacks is 3 x 10(-3) and 9 x 10(-3) cm2/(V s) for holes and electrons, respectively. Additionally, we have calculated the mobility along the pi-stacks using a hopping model based on parameters from density functional theory. The mobility values obtained from these calculations are in good agreement with the experimental values if it is assumed that there are relatively large twist angles between neighboring molecules in the stack. It is shown that a significantly higher mobility can be attained if the twist angle between neighboring oligomers is reduced.

Intensity modulated radiation therapy planning for patients with a metal hip prosthesis based on class solutions.

PURPOSE: With the aging of the population, an increasing number of patients with metallic hip implants are referred for radiotherapy treatment. Class solutions for intensity modulated radiation therapy (IMRT) treatment planning are generally not applicable for these patients due to the required avoidance of dose delivery through prostheses. In this work a new approach for IMRT planning is presented, allowing the use of a default beam setup. METHODS AND MATERIALS: For IMRT planning, Monaco (Elekta; CMS Software, Maryland Heights, MO) was used. In addition to the target and organs at risk, so-called prosthesis avoidance volumes (PAVs) were delineated in the beam's eye view projection for beams in which the prosthesis was partially in front of the target. By putting strict constraints on these virtual organs at risk, entrance dose delivery through a prosthesis is avoided while exit dose delivery is allowed. In this way, uncertainties in the dose delivery to the target and organs at risk, as derived by the treatment planning system, are largely minimized. To show the advantages of this IMRT-PAV technique, for 2 prostate cancer patients, 1 with bilateral and the other with unilateral metallic hip prostheses, obtained IMRT plans were compared with conventional IMRT plans using a prosthesis-avoiding beam setup. RESULTS: For both IMRT techniques a similar planning target volume coverage was achieved, but with the IMRT-PAV technique the mean doses to the bladder and the rectum were reduced by up to 25%. While the IMRT-PAV technique required more time for delineation, the time for treatment planning reduced because the default beam setup could be applied. The number of segments needed for dose delivery was comparable for both techniques. CONCLUSIONS: With the new IMRT-PAV technique IMRT class solutions can safely be applied for cancer patients with metallic hip prostheses, generally yielding a reduced dose delivery to organs at risk or improved target coverage.

Photoluminescence and conductivity of self-assembled pi-pi stacks of perylene bisimide dyes.

The self-assembly of a new, highly fluorescent perylene bisimide dye 2 into pi stacks, both in solution and condensed phase, has been studied in detail by NMR spectroscopy, vapor pressure osmometry (VPO), UV/Vis and fluorescence spectroscopy, differential scanning calorimetry (DSC), optical polarizing microscopy (OPM) and X-ray diffraction. The NMR and VPO measurements revealed the formation of extended pi-pi stacks of the dye molecules in solution. The aggregate size determined from VPO and DOSY NMR measurements agree well with that obtained from the concentration and temperature-dependent UV/Vis spectral data by employing the isodesmic model (equal K model). In the condensed state, dye 2 possesses a hexagonal columnar liquid crystalline (LC) phase as confirmed by X-ray diffraction analysis. The columnar stacking of this dye has been further explored by atomic force microscopy (AFM). Well-resolved columnar nanostructures of the compound are observed on graphite surface. A color-tunable luminescence from green to red has been observed upon aggregation which is accompanied by an increase of the fluorescence lifetime and depolarization. The observed absorption properties can be explained in terms of molecular exciton theory. The charge transport properties of dye 2 have been investigated by pulse radiolysis-time resolved microwave conductivity measurements and a 1D charge carrier mobility up to 0.42 cm(2) V(-1) s(-1) is obtained. Considering the promising self-assembly, semiconducting, and luminescence properties of this dye, it might serve as a useful functional material for nano(opto)electronics.