Theoretical study of two states reactivity of methane activation on iron atom and iron dimer

Density functional theory (DFT) calculations have been carried out to explore the catalytic activation of C–H bonds in methane by the iron atom, Fe, and the iron dimer, Fe2. For methane activation on an Fe atom, the calculations suggest that the activation of the first C–H bond is mediated via the triplet excited-state potential energy surface (PES), with initial excitation of Fe to the triplet state being necessary for the reaction to be energetically feasible. Compared with the breaking of the first C–H bond, the cleavage of the second C–H bond is predicted to involve a significantly higher barrier, which could explain experimental observations of the HFeCH3 complex rather than CH2FeH2 in the activation of methane by an Fe atom. For methane activation on an iron dimer, the cleavage of the first C–H bond is quite facile with a barrier only 11.2, 15.8 and 8.4 kcal/mol on the septet state energy surface at the B3LYP/6-311+G(2df,2dp), BPW91/6-311+G(2df,2dp) and M06/B3LYP level, respectively. Cleavage of the second C–H bond from HFe2CH3 involves a barrier calculated respectively as 18.0, 10.7 and 12.4 kcal/mol at the three levels. The results suggest that the elimination of hydrogen from the dihydrogen complex is a rate-determining step. Overall, our results indicate that the iron dimer Fe2 has a stronger catalytic effect on the activation of methane than the iron atom.

Data warehousing model for integrating fragmented electronic health records from disparate and heterogeneous clinical data stores

This research was a step forward in developing a data integration framework for Electronic Health Records. The outcome of the research is a conceptual and logical Data Warehousing model for integrating Cardiac Surgery electronic data records. This thesis investigated the main obstacles for the healthcare data integration and proposes a data warehousing model suitable for integrating fragmented data in a Cardiac Surgery Unit.

Verification of patient position and delivery of IMRT by electronic portal imaging

Background and purpose: The purpose of the work presented in this paper was to determine whether patient positioning and delivery errors could be detected using electronic portal images of intensity modulated radiotherapy (IMRT). Patients and methods: We carried out a series of controlled experiments delivering an IMRT beam to a humanoid phantom using both the dynamic and multiple static field method of delivery. The beams were imaged, the images calibrated to remove the IMRT fluence variation and then compared with calibrated images of the reference beams without any delivery or position errors. The first set of experiments involved translating the position of the phantom both laterally and in a superior/inferior direction a distance of 1, 2, 5 and 10 mm. The phantom was also rotated 1 and 28. For the second set of measurements the phantom position was kept fixed and delivery errors were introduced to the beam. The delivery errors took the form of leaf position and segment intensity errors. Results: The method was able to detect shifts in the phantom position of 1 mm, leaf position errors of 2 mm, and dosimetry errors of 10% on a single segment of a 15 segment IMRT step and shoot delivery (significantly less than 1% of the total dose). Conclusions: The results of this work have shown that the method of imaging the IMRT beam and calibrating the images to remove the intensity modulations could be a useful tool in verifying both the patient position and the delivery of the beam.

The use of electronic portal imaging to verify patient position during intensity-modulated radiotherapy delivered by the dynamic MLC technique

Purpose: The precise shape of the three-dimensional dose distributions created by intensity-modulated radiotherapy means that the verification of patient position and setup is crucial to the outcome of the treatment. In this paper, we investigate and compare the use of two different image calibration procedures that allow extraction of patient anatomy from measured electronic portal images of intensity-modulated treatment beams. Methods and Materials: Electronic portal images of the intensity-modulated treatment beam delivered using the dynamic multileaf collimator technique were acquired. The images were formed by measuring a series of frames or segments throughout the delivery of the beams. The frames were then summed to produce an integrated portal image of the delivered beam. Two different methods for calibrating the integrated image were investigated with the aim of removing the intensity modulations of the beam. The first involved a simple point-by-point division of the integrated image by a single calibration image of the intensity-modulated beam delivered to a homogeneous polymethyl methacrylate (PMMA) phantom. The second calibration method is known as the quadratic calibration method and required a series of calibration images of the intensity-modulated beam delivered to different thicknesses of homogeneous PMMA blocks. Measurements were made using two different detector systems: a Varian amorphous silicon flat-panel imager and a Theraview camera-based system. The methods were tested first using a contrast phantom before images were acquired of intensity-modulated radiotherapy treatment delivered to the prostate and pelvic nodes of cancer patients at the Royal Marsden Hospital. Results: The results indicate that the calibration methods can be used to remove the intensity modulations of the beam, making it possible to see the outlines of bony anatomy that could be used for patient position verification. This was shown for both posterior and lateral delivered fields. Conclusions: Very little difference between the two calibration methods was observed, so the simpler division method, requiring only the single extra calibration measurement and much simpler computation, was the favored method. This new method could provide a complementary tool to existing position verification methods, and it has the advantage that it is completely passive, requiring no further dose to the patient and using only the treatment fields.

First-principle studies of electronic structure and C-doping effect in boron nitride nanoribbon

Structural and electronic properties have been studied for Boron Nitride nanoribbons (BNNR) with both zigzag and armchair shaped edge (Z-BNNR and A-BNNR) by first-principle spin-polarized total energy calculations. We found that the energy band gap of Z-BNNR is indirect and decreases monotonically with the increasing ribbon width, whereas direct energy band gap oscillation was observed for A-BNNRs. Additionally, C-substitution at either single boron or nitrogen atom site in BNNRs could induce spontaneous magnetization. Our results could be potentially useful to design magnetic nano-devices based on BNNRs.

Structural and electronic properties of diazonium functionalized (4, 4) single walled carbon nanotube : an ab initio study

In this work, ab initio density functional theory (DFT) calculations are performed to study the structural and electronic properties of diazonium reagent functionalized (4, 4) single-walled carbon nanotube (SWCNT). We find the aryl group covalently bonds with SWCNT and prefers to be perpendicular to the side wall of nanotube. It has a rotational barrier of 0.35 eV around the formed aryl-tube bond axis and should be thermodynamically stable at room temperature. Additionally, new peaks appeared around the Fermi energy in the density of state (DOS) due to the weak band dispersion. Increasing of the coverage of the functional group will result in significant upshift of the Fermi level.

Adatom CCV Auger rates via the local density of states

In this letter the core-core-valence Auger transitions of an atomic impurity, both in bulk or adsorbed on a jellium-like surface, are computed within a DFT framework. The Auger rates calculated by the Fermi golden rule are compared with those determined by an approximate and simpler expression. This is based on the local density of states (LDOS) with a core hole present, in a region around the impurity nucleus. Different atoms, Na and Mg, solids, Al and Ag, and several impurity locations are considered. We obtain an excellent agreement between KL1V and KL23V rates worked out with the two approaches. The radius of the sphere in which we calculate the LDOS is the relevant parameter of the simpler approach. Its value only depends on the atomic species regardless of the location of the impurity and the type of substrate. (C) 2003 Elsevier B.V. All rights reserved.

Beat-mixing Rock music: Rock and electronic dance music merge to create the Manarays

This research introduces the proposition that Electronic Dance Music’s beat-mixing function could be implemented to create immediacy in other musical genres. The inclusion of rhythmic sections at the beginning and end of each musical work created a ‘DJ friendly’ environment. The term used in this thesis to refer to the application of beat-mixing in Rock music is ‘ClubRock’. Collaboration between a number of DJs and Rock music professionals applied the process of beat-mixing to blend Rock tracks to produce a continuous ClubRock set. The DJ technique of beat-mixing Rock music transformed static renditions into a fluid creative work. The hybridisation of the two genres, EDM and Rock, resulted in a contribution to Rock music compositional approaches and the production of a unique Rock album; Manarays—Get Lucky.

The role of perceived usefulness and attitude on electronic health record acceptance : an empirical investigation using response surface analysis

Information and communications technologies are a significant component of the healthcare domain and electronic health records play a major role within it. As a result, it is important that they are accepted en masse by healthcare professionals. How healthcare professionals perceive the usefulness of electronic health records and their attitudes towards them have been shown to have significant effects on their overall acceptance. This paper investigates the role of perceived usefulness and attitude on the intention to use electronic health records by future healthcare professionals using polynomial regression with response surface analysis. Results show that the relationship is more complex than predicted in prior research. The paper concludes that the predicting properties of the above determinants must be further investigated to clearly understand their role in predicting the intention to use electronic health records and in designing systems that are better adopted by healthcare professionals of the future.

Investigation of megavoltage beams and detectors for electronic portal imaging

Accuracy of dose delivery in external beam radiotherapy is usually verified with electronic portal imaging (EPI) in which the treatment beam is used to check the positioning of the patient. However the resulting megavoltage x-ray images suffer from poor quality. The image quality can be improved by developing a special operating mode in the linear accelerator. The existing treatment beam is modified such that it produces enough low-energy photons for imaging. In this work the problem of optimizing the beam/detector combination to achieve optimal electronic portal image quality is addressed. The linac used for this study was modified to produce two experimental photon beams. These beams, named Al6 and Al10, were non-flat and were produced by 4MeV electrons hitting aluminum targets, 6 and 10mm thick respectively. The images produced by a conventional EPI system (6MV treatment beam and camera-based EPID with a Cu plate & Gd2O2S screen ) were compared with the images produced by the experimental beams and various screens with the same camera). The contrast of 0.8cm bone equivalent material in 5 cm water increased from 1.5% for the conventional system to 11% for the combination of Al6 beam with a 200mg/cm2 Gd2O2S screen. The signal-to-noise ratio calculated for 1cGy flood field images increased by about a factor of two for the same EPI systems. The spatial resolution of the two imaging systems was comparable. This work demonstrates that significant improvements in portal image contrast can be obtained by simultaneous optimization of the linac spectrum and EPI detector.

Verification of patient position and delivery of IMRT by electronic Portal Imaging

We have taken a new method of calibrating portal images of IMRT beams and used this to measure patient set-up accuracy and delivery errors, such as leaf errors and segment intensity errors during treatment. A calibration technique was used to remove the intensity modulations from the images leaving equivalent open field images that show patient anatomy that can be used for verification of the patient position. The images of the treatment beam can also be used to verify the delivery of the beam in terms of multileaf collimator leaf position and dosimetric errors. A series of controlled experiments delivering an IMRT anterior beam to the head and neck of a humanoid phantom were undertaken. A 2mm translation in the position of the phantom could be detected. With intentional introduction of delivery errors into the beam this method allowed us to detect leaf positioning errors of 2mm and variation in monitor units of 1%. The method was then applied to the case of a patient who received IMRT treatment to the larynx and cervical nodes. The anterior IMRT beam was imaged during four fractions and the images calibrated and investigated for the characteristic signs of patient position error and delivery error that were shown in the control experiments. No significant errors were seen. The method of imaging the IMRT beam and calibrating the images to remove the intensity modulations can be a useful tool in verifying both the patient position and the delivery of the beam.