985 resultados para proton-transfer compounds


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Numerical simulations of thermomagnetic convection of paramagnetic fluids placed in a micro-gravity condition (g ≈ 0) and under a uniform vertical gradient magnetic field in an open ended square enclosure with ramp heating temperature condition applied on a vertical wall is investigated in this study. In presence of the strong magnetic gradient field thermal convection of the paramagnetic fluid might take place even in a zero-gravity environment as a direct consequence of temperature differences occurring within the fluid. The thermal boundary layer develops adjacent to the hot wall as soon as the ramp temperature condition is applied on it. There are two scenarios can be observed based on the ramp heating time. The steady state of the thermal boundary layer can be reached before the ramp time is finished or vice versa. If the ramp time is larger than the quasi-steady time then the thermal boundary layer is in a quasi-steady mode with convection balancing conduction after the quasi-steady time. Further increase of the heat input simply accelerates the flow to maintain the proper thermal balance. Finally, the boundary layer becomes completely steady state when the ramp time is finished. Effects of magnetic Rayleigh number, Prandtl number and paramagnetic fluid parameter on the flow pattern and heat transfer are presented.

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Stagnation-point total heat transfer was measured on a 1:27.7 model of the Flight Investigation of Reentry Environment II flight vehicle. Experiments were performed in the X1 expansion tube at an equivalent flight velocity and static enthalpy of 11 km/s and 12.7 MJ/kg, respectively. Conditions were chosen to replicate the flight condition at a total flight time of 1639.5 s, where radiation contributed an estimated 17-36% of the total heat transfer. This contribution is theorized to reduce to <2% in the scaled experiments, and the heating environment on the test model was expected to be dominated by convection. A correlation between reported flight heating rates and expected experimental heating, referred to as the reduced flight value, was developed to predict the level of heating expected on the test model. At the given flow conditions, the reduced flight value was calculated to be 150 MW/m2. Average stagnation-point total heat transfer was measured to be 140 ± 7% W/m2, showing good agreement with the predicted value. Experimentally measured heat transfer was found to have good agreement of between 5 and 15% with a number of convective heating correlations, confirming that convection dominates the tunnel heating environment, and that useful experimental measurements could be made in weakly coupled radiating flow

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The international tax system, designed a century ago, has not kept pace with the modern multinational entity rendering it ineffective in taxing many modern businesses according to economic activity. One of those modern multinational entities is the multinational financial institution (MNFI). The recent global financial crisis provides a particularly relevant and significant example of the failure of the current system on a global scale. The modern MNFI is increasingly undertaking more globalised and complex trading operations. A primary reason for the globalisation of financial institutions is that they typically ‘follow-the-customer’ into jurisdictions where international capital and international investors are required. The International Monetary Fund (IMF) recently reported that from 1995-2009, foreign bank presence in developing countries grew by 122 per cent. The same study indicates that foreign banks have a 20 per cent market share in OECD countries and 50 per cent in emerging markets and developing countries. Hence, most significant is that fact that MNFIs are increasingly undertaking an intermediary role in developing economies where they are financing core business activities such as mining and tourism. IMF analysis also suggests that in the future, foreign bank expansion will be greatest in emerging economies. The difficulties for developing countries in applying current international tax rules, especially the current traditional transfer pricing regime, are particularly acute in relation to MNFIs, which are the biggest users of tax havens and offshore finance. This paper investigates whether a unitary taxation approach which reflects economic reality would more easily and effectively ensure that the profits of MNFIs are taxed in the jurisdictions which give rise to those profits. It has previously been argued that the uniqueness of MNFIs results in a failure of the current system to accurately allocate profits and that unitary tax as an alternative could provide a sounder allocation model for international tax purposes. This paper goes a step further, and examines the practicalities of the implementation of unitary taxation for MNFIs in terms of the key components of such a regime, along with their their implications. This paper adopts a two-step approach in considering the implications of unitary taxation as a means of improved corporate tax coordination which requires international acceptance and agreement. First, the definitional issues of the unitary MNFI are examined and second, an appropriate allocation formula for this sector is investigated. To achieve this, the paper asks first, how the financial sector should be defined for the purposes of unitary taxation and what should constitute a unitary business for that sector and second, what is the ‘best practice’ model of an allocation formula for the purposes of the apportionment of the profits of the unitary business of a financial institution.

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In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

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Background The transfer and/or retrieval of a critically patient is inherently dangerous not only for the patient but for staff as well. The quality and experience of unplanned transfers can influence patient mortality and morbidity. However, international evidence suggests that dedicated transfer/retrieval teams can improve mortality and morbidity outcomes. Aims The initial aim of this paper is to describe an in-house competency-based training programme, which encompasses the STaR approach to develop members of our existing nursing team to be part of the dedicated transfer/retrieval service. The paper also presents audit data findings which examined the source of referrals, number of patients actually transferred and clinical status of those being transferred. Results Audit data illustrate that the most frequent source of referrals comes from Accident and Emergency and the Surgical Directorate with the most common presenting condition being cardio-respiratory failure or arrest. Audit data reveal that the number of patients actually transferred or retrieved is relatively small (33%) compared with the overall number of requests for assistance. However, 36% of those patients transferred had a level 2 or level 3 acuity status that necessitated the admission to a critical care area. Conclusions A number of studies have concluded that the ill-experienced and ill-equipped transfer team can place patients’ at serious risk of harm. Whether planned or unplanned, dedicated critical care transfer/retrieval teams have been shown to reduce patient mortality and morbidity.

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The notion of sovereignty is central to any international tax issue. While a nation is free to design its tax laws as it sees fit and raise revenue in accordance with the needs of its citizens, it is not possible to undertake such a task in isolation. Tax interactions between sovereign states cannot be avoided. Ultimately, the interactions mean that a nation must decide whether or engage in both collaboration and co ordination with other nations and supranational bodies alike or maintain a unilateral stance in relation to its tax policy. This article considers a modern conceptualisation of sovereignty to argue that a move towards a more unified approach to addressing international base erosion and profit sharing may be the ultimate exercise of national fiscal sovereignty.

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The thesis provides an Indonesian perspective into the rationales and outcomes of cooperation between Indonesian and Australian universities. It demonstrates that Indonesian universities participating in this study have actively pursued their institutional agenda to bring benefits from the cooperation with the international partners and engaged in knowledge transfer with these partners to develop their capacity. It particularly investigates the knowledge transfer processes between Indonesian and Australian universities through dual degree program partnerships.

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The present article gives an overview of the reversible addition fragmentation chain transfer (RAFT) process. RAFT is one of the most versatile living radical polymerization systems and yields polymers of predictable chain length and narrow molecular weight distribution. RAFT relies on the rapid exchange of thiocarbonyl thio groups between growing polymeric chains. The key strengths of the RAFT process for polymer design are its high tolerance of monomer functionality and reaction conditions, the wide range of well-controlled polymeric architectures achievable, and its (in-principle) non-rate-retarding nature. This article introduces the mechanism of polymerization, the range of polymer molecular weights achievable, the range of monomers in which polymerization is controlled by RAFT, the various polymeric architectures that can be obtained, the type of end-group functionalities available to RAFT-made polymers, and the process of RAFT polymerization.

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Radiative and total heat transfer at the flow stagnation point of a 1:40.8 binary scaled model of the Titan Explorer vehicle were measured in the X3 expansion tube. Results from the current study illustrated that with the addition of CH4 into a N2 test gas radiative heat transfer could be detected. For a test gas of 5% CH4 and 95% N2, simulating an atmospheric model for Titanic aerocapture, approximately 4% of the experimentally measured total stagnation point heat transfer was found to be due to radiation. This was in comparison to < 1% measured for a test gas of pure nitrogen. When scaled to the flight vehicle, experimental results indicate a 64% contribution of radiation (test gas 5% CH4/95% N2). Previous numerical results however have predicted this contribution to be between 80-92%. Thus, experimental results from the current study suggest that numerical analyses are over-predicting the radiative heat transfer on the flight vehicle.

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The present study focused on simulating a trajectory point towards the end of the first experimental heatshield of the FIRE II vehicle, at a total flight time of 1639.53s. Scale replicas were sized according to binary scaling and instrumented with thermocouples for testing in the X1 expansion tube, located at The University of Queensland. Correlation of flight to experimental data was achieved through the separation, and independent treatment of the heat modes. Preliminary investigation indicates that the absolute value of radiant surface flux is conserved between two binary scaled models, whereas convective heat transfer increases with the length scale. This difference in the scaling techniques result in the overall contribution of radiative heat transfer diminishing to less than 1% in expansion tubes from a flight value of approximately 9-17%. From empirical correlation's it has been shown that the St √Re number decreases, under special circumstances, in expansion tubes by the percentage radiation present on the flight vehicle. Results obtained in this study give a strong indication that the relative radiative heat transfer contribution in the expansion tube tests is less than that in flight, supporting the analysis that the absolute value remains constant with binary scaling.

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Nuclei and electrons in condensed matter and/or molecules are usually entangled, due to the prevailing (mainly electromagnetic) interactions. However, the "environment" of a microscopic scattering system (e.g. a proton) causes ultrafast decoherence, thus making atomic and/or nuclear entanglement e®ects not directly accessible to experiments. However, our neutron Compton scattering experiments from protons (H-atoms) in condensed systems and molecules have a characteristic collisional time about 100|1000 attoseconds. The quantum dynamics of an atom in this ultrashort, but ¯nite, time window is governed by non-unitary time evolution due to the aforementioned decoherence. Unexpectedly, recent theoretical investigations have shown that decoherence can also have the following energetic consequences. Disentangling two subsystems A and B of a quantum system AB is tantamount to erasure of quantum phase relations between A and B. This erasure is widely believed to be an innocuous process, which e.g. does not a®ect the energies of A and B. However, two independent groups proved recently that disentangling two systems, within a su±ciently short time interval, causes increase of their energies. This is also derivable by the simplest Lindblad-type master equation of one particle being subject to pure decoherence. Our neutron-proton scattering experiments with H2 molecules provide for the first time experimental evidence of this e®ect. Our results reveal that the neutron-proton collision, leading to the cleavage of the H-H bond in the attosecond timescale, is accompanied by larger energy transfer (by about 2|3%) than conventional theory predicts. Preliminary results from current investigations show qualitatively the same e®ect in the neutron-deuteron Compton scattering from D2 molecules. We interpret the experimental findings by treating the neutron-proton (or neutron-deuteron) collisional system as an entangled open quantum system being subject to fast decoherence caused by its "environment" (i.e., two electrons plus second nucleus of H2 or D2). The presented results seem to be of generic nature, and may have considerable consequences for various processes in condensed matter and molecules, e.g. in elementary chemical reactions.

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Decoherence of quantum entangled particles is observed in most systems, and is usually caused by system-environment interactions. Disentangling two subsystems A and B of a quantum systemAB is tantamount to erasure of quantum phase relations between A and B. It is widely believed that this erasure is an innocuous process, which e.g. does not affect the energies of A and B. Surprisingly, recent theoretical investigations by different groups showed that disentangling two systems, i.e. their decoherence, can cause an increase of their energies. Applying this result to the context of neutronCompton scattering from H2 molecules, we provide for the first time experimental evidence which supports this prediction. The results reveal that the neutron-proton collision leading to the cleavage of the H-H bond in the sub-femtosecond timescale is accompanied by larger energy transfer (by about 3%) than conventional theory predicts. It is proposed to interpreted the results by considering the neutron-proton collisional system as an entangled open quantum system being subject to decoherence owing to the interactions with the “environment” (i.e., two electrons plus second proton of H2).

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The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.