15 resultados para REVERSIBILITY

em Queensland University of Technology - ePrints Archive


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Purpose: The development of liver metastases from breast cancer is associated with a very poor prognosis, estimated at 4 months median survival. Since treatment with many chemotherapeutic agents is relatively contraindicated, we assessed the safety, tolerability and potential efficacy of combination chemotherapy with vinorelbine and cisplatin (ViP). Method: Pilot study in 11 patients with histologically confirmed breast carcinoma, radiological evidence of liver metastases and serum bilirubin greater than 1.5 times the upper limit of normal. Patients received up to six cycles of cisplatin (75 mg/m 2) every 21 days and vinorelbine (20 mg/m 2) on days 1 and 8 of every 21-day cycle. Measurement of liver lesions was performed on CT scan every 8 weeks into treatment. Results: The most frequently reported adverse event was myelosuppression. Other adverse effects included nausea, vomiting and mild neurotoxicity. Two patients died after one treatment with ViP, one of whom suffered an intracerebral haemorrhage that was possibly treatment-related. Improvement in liver function tests was observed in 10 patients, and mean time to normalization of bilirubin levels was 36 days. Partial responses were documented radiologically in 7 out of 11 patients treated. Median overall survival from trial entry was 6.5 months (range 11-364 days), with one patient alive 13 months from trial entry. Conclusion: Normalization of liver function is possible with ViP treatment of metastatic breast cancer, offering the potential to prolong survival. Phase II clinical trials of this regimen in this patient group should include measurement of quality of life in order to assess risk versus benefit.

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Traditional approaches to nonmonotonic reasoning fail to satisfy a number of plausible axioms for belief revision and suffer from conceptual difficulties as well. Recent work on ranked preferential models (RPMs) promises to overcome some of these difficulties. Here we show that RPMs are not adequate to handle iterated belief change. Specifically, we show that RPMs do not always allow for the reversibility of belief change. This result indicates the need for numerical strengths of belief.

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Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Objectives This prospective study investigated the effects of caffeine ingestion on the extent of adenosine-induced perfusion abnormalities during myocardial perfusion imaging (MPI). Methods Thirty patients with inducible perfusion abnormalities on standard (caffeine-abstinent) adenosine MPI underwent repeat testing with supplementary coffee intake. Baseline and test MPIs were assessed for stress percent defect, rest percent defect, and percent defect reversibility. Plasma levels of caffeine and metabolites were assessed on both occasions and correlated with MPI findings. Results Despite significant increases in caffeine [mean difference 3,106 μg/L (95% CI 2,460 to 3,752 μg/L; P < .001)] and metabolite concentrations over a wide range, there was no statistically significant change in stress percent defect and percent defect reversibility between the baseline and test scans. The increase in caffeine concentration between the baseline and the test phases did not affect percent defect reversibility (average change −0.003 for every 100 μg/L increase; 95% CI −0.17 to 0.16; P = .97). Conclusion There was no significant relationship between the extent of adenosine-induced coronary flow heterogeneity and the serum concentration of caffeine or its principal metabolites. Hence, the stringent requirements for prolonged abstinence from caffeine before adenosine MPI—based on limited studies—appear ill-founded.

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Recent experiments [F. E. Pinkerton, M. S. Meyer, G. P. Meisner, M. P. Balogh, and J. J. Vajo, J. Phys. Chem. C 111, 12881 (2007) and J. J. Vajo and G. L. Olson, Scripta Mater. 56, 829 (2007)] demonstrated that the recycling of hydrogen in the coupled LiBH4/MgH2 system is fully reversible. The rehydrogenation of MgB2 is an important step toward the reversibility. By using ab initio density functional theory calculations, we found that the activation barrier for the dissociation of H2 are 0.49 and 0.58 eV for the B and Mg-terminated MgB2(0001) surface, respectively. This implies that the dissociation kinetics of H2 on a MgB2 (0001) surface should be greatly improved compared to that in pure Mg materials. Additionally, the diffusion of dissociated H atom on the Mg-terminated MgB2(0001) surface is almost barrier-less. Our results shed light on the experimentally-observed reversibility and improved kinetics for the coupled LiBH4/MgH2 system.

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The structures and thermodynamic properties of methyl derivatives of ammonia–borane (BH3NH3, AB) have been studied with the frameworks of density functional theory and second-order Møller–Plesset perturbation theory. It is found that, with respect to pure AB, methyl ammonia–boranes show higher complexation energies and lower reaction enthalpies for the release of H2, together with a slight increment of the activation barrier. These results indicate that the methyl substitution can enhance the reversibility of the system and prevent the formation of BH3/NH3, but no enhancement of the release rate of H2 can be expected.

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Numeric set watermarking is a way to provide ownership proof for numerical data. Numerical data can be considered to be primitives for multimedia types such as images and videos since they are organized forms of numeric information. Thereby, the capability to watermark numerical data directly implies the capability to watermark multimedia objects and discourage information theft on social networking sites and the Internet in general. Unfortunately, there has been very limited research done in the field of numeric set watermarking due to underlying limitations in terms of number of items in the set and LSBs in each item available for watermarking. In 2009, Gupta et al. proposed a numeric set watermarking model that embeds watermark bits in the items of the set based on a hash value of the items’ most significant bits (MSBs). If an item is chosen for watermarking, a watermark bit is embedded in the least significant bits, and the replaced bit is inserted in the fractional value to provide reversibility. The authors show their scheme to be resilient against the traditional subset addition, deletion, and modification attacks as well as secondary watermarking attacks. In this paper, we present a bucket attack on this watermarking model. The attack consists of creating buckets of items with the same MSBs and determine if the items of the bucket carry watermark bits. Experimental results show that the bucket attack is very strong and destroys the entire watermark with close to 100% success rate. We examine the inherent weaknesses in the watermarking model of Gupta et al. that leave it vulnerable to the bucket attack and propose potential safeguards that can provide resilience against this attack.

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There has been significant research in the field of database watermarking recently. However, there has not been sufficient attention given to the requirement of providing reversibility (the ability to revert back to original relation from watermarked relation) and blindness (not needing the original relation for detection purpose) at the same time. This model has several disadvantages over reversible and blind watermarking (requiring only the watermarked relation and secret key from which the watermark is detected and the original relation is restored) including the inability to identify the rightful owner in case of successful secondary watermarking, the inability to revert the relation to the original data set (required in high precision industries) and the requirement to store the unmarked relation at a secure secondary storage. To overcome these problems, we propose a watermarking scheme that is reversible as well as blind. We utilize difference expansion on integers to achieve reversibility. The major advantages provided by our scheme are reversibility to a high quality original data set, rightful owner identification, resistance against secondary watermarking attacks, and no need to store the original database at a secure secondary storage. We have implemented our scheme and results show the success rate is limited to 11% even when 48% tuples are modified.

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There has been significant research in the field of database watermarking recently. However, there has not been sufficient attention given to the requirement of providing reversibility (the ability to revert back to original relation from watermarked relation) and blindness (not needing the original relation for detection purpose) at the same time. This model has several disadvantages over reversible and blind watermarking (requiring only the watermarked relation and secret key from which the watermark is detected and the original relation is restored) including the inability to identify the rightful owner in case of successful secondary watermarking, the inability to revert the relation to the original data set (required in high precision industries) and the requirement to store the unmarked relation at a secure secondary storage. To overcome these problems, we propose a watermarking scheme that is reversible as well as blind. We utilize difference expansion on integers to achieve reversibility. The major advantages provided by our scheme are reversibility to a high quality original data set, rightful owner identification, resistance against secondary watermarking attacks, and no need to store the original database at a secure secondary storage. We have implemented our scheme and results show the success rate is limited to 11% even when 48% tuples are modified.

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There has been tremendous interest in watermarking multimedia content during the past two decades, mainly for proving ownership and detecting tamper. Digital fingerprinting, that deals with identifying malicious user(s), has also received significant attention. While extensive work has been carried out in watermarking of images, other multimedia objects still have enormous research potential. Watermarking database relations is one of the several areas which demand research focus owing to the commercial implications of database theft. Recently, there has been little progress in database watermarking, with most of the watermarking schemes modeled after the irreversible database watermarking scheme proposed by Agrawal and Kiernan. Reversibility is the ability to re-generate the original (unmarked) relation from the watermarked relation using a secret key. As explained in our paper, reversible watermarking schemes provide greater security against secondary watermarking attacks, where an attacker watermarks an already marked relation in an attempt to erase the original watermark. This paper proposes an improvement over the reversible and blind watermarking scheme presented in [5], identifying and eliminating a critical problem with the previous model. Experiments showing that the average watermark detection rate is around 91% even with attacker distorting half of the attributes. The current scheme provides security against secondary watermarking attacks.

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Database watermarking has received significant research attention in the current decade. Although, almost all watermarking models have been either irreversible (the original relation cannot be restored from the watermarked relation) and/or non-blind (requiring original relation to detect the watermark in watermarked relation). This model has several disadvantages over reversible and blind watermarking (requiring only watermarked relation and secret key from which the watermark is detected and original relation is restored) including inability to identify rightful owner in case of successful secondary watermarking, inability to revert the relation to original data set (required in high precision industries) and requirement to store unmarked relation at a secure secondary storage. To overcome these problems, we propose a watermarking scheme that is reversible as well as blind. We utilize difference expansion on integers to achieve reversibility. The major advantages provided by our scheme are reversibility to high quality original data set, rightful owner identification, resistance against secondary watermarking attacks, and no need to store original database at a secure secondary storage.

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Database watermarking has received significant research attention in the current decade. Although, almost all watermarking models have been either irreversible (the original relation cannot be restored from the watermarked relation) and/or non-blind (requiring original relation to detect the watermark in watermarked relation). This model has several disadvantages over reversible and blind watermarking (requiring only watermarked relation and secret key from which the watermark is detected and original relation is restored) including inability to identify rightful owner in case of successful secondary watermarking, inability to revert the relation to original data set (required in high precision industries) and requirement to store unmarked relation at a secure secondary storage. To overcome these problems, we propose a watermarking scheme that is reversible as well as blind. We utilize difference expansion on integers to achieve reversibility. The major advantages provided by our scheme are reversibility to high quality original data set, rightful owner identification, resistance against secondary watermarking attacks, and no need to store original database at a secure secondary storage.

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In this paper, we look at the concept of reversibility, that is, negating opposites, counterbalances, and actions that can be reversed. Piaget identified reversibility as an indicator of the ability to reason at a concrete operational level. We investigate to what degree novice programmers manifest the ability to work with this concept of reversibility by providing them with a small piece of code and then asking them to write code that undoes the effect of that code. On testing entire cohorts of students in their first year of learning to program, we found an overwhelming majority of them could not cope with such a concept. We then conducted think aloud studies of novices where we observed them working on this task and analyzed their contrasting abilities to deal with it. The results of this study demonstrate the need for better understanding our students' reasoning abilities, and a teaching model aimed at that level of reality.

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The single electron transfer-nitroxide radical coupling (SET-NRC) reaction has been used to produce multiblock polymers with high molecular weights in under 3 min at 50◦C by coupling a difunctional telechelic polystyrene (Br-PSTY-Br)with a dinitroxide. The well known combination of dimethyl sulfoxide as solvent and Me6TREN as ligand facilitated the in situ disproportionation of CuIBr to the highly active nascent Cu0 species. This SET reaction allowed polymeric radicals to be rapidly formed from their corresponding halide end-groups. Trapping of these carbon-centred radicals at close to diffusion controlled rates by dinitroxides resulted in high-molecular-weight multiblock polymers. Our results showed that the disproportionation of CuI was critical in obtaining these ultrafast reactions, and confirmed that activation was primarily through Cu0. We took advantage of the reversibility of the NRC reaction at elevated temperatures to decouple the multiblock back to the original PSTY building block through capping the chain-ends with mono-functional nitroxides. These alkoxyamine end-groups were further exchanged with an alkyne mono-functional nitroxide (TEMPO–≡) and ‘clicked’ by a CuI-catalyzed azide/alkyne cycloaddition (CuAAC) reaction with N3–PSTY–N3 to reform the multiblocks. This final ‘click’ reaction, even after the consecutive decoupling and nitroxide-exchange reactions, still produced high molecular-weight multiblocks efficiently. These SET-NRC reactions would have ideal applications in re-usable plastics and possibly as self-healing materials.

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High activation of polystyrene with bromine end groups (PSTY-Br) to their incipient radicals occurred in the presence of Cu(I)Br, Me6TREN, and DMSO solvent. These radicals were then trapped by nitroxide species leading to coupling reactions between PSTY-Br and nitroxides that were ultrafast and selective in the presence of a diverse range of functional groups. The nitroxide radical coupling (NRC) reactions have the attributes of a “click” reaction with near quantitative yields of product formed, but through the reversibility of this reaction, it has the added advantage of permitting the exchange of chemical functionality on macromolecules. Conditions were chosen to facilitate the disproportionation of Cu(I)Br to the highly activating nascent Cu(0) and deactivating Cu(II)Br2 in the presence of DMSO solvent and Me6TREN ligand. NRC at room temperature gave near quantitative yields of macromolecular coupling of low molecular weight polystyrene with bromine chain-ends (PSTY-Br) and nitroxides in under 7 min even in the presence of functional groups (e.g., −≡, −OH, −COOH, −NH2, =O). Utilization of the reversibility of the NRC reaction at elevated temperatures allowed the exchange of chain-end groups with a variety of functional nitroxide derivatives. The robustness and orthogonality of this NRC reaction were further demonstrated using the Cu-catalyzed azide/alkyne “click” (CuAAC) reactions, in which yields greater than 95% were observed for coupling between PSTY-N3 and a PSTY chain first trapped with an alkyne functional TEMPO (PSTY-TEMPO-≡).