4 resultados para Methods in tourism

em ArchiMeD - Elektronische Publikationen der Universität Mainz - Alemanha


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This thesis is focused on the development of heteronuclear correlation methods in solid-state NMR spectroscopy, where the spatial dependence of the dipolar coupling is exploited to obtain structural and dynamical information in solids. Quantitative results on dipolar coupling constants are extracted by means of spinning sideband analysis in the indirect dimension of the two-dimensional experiments. The principles of sideband analysis were established and are currently widely used in the group of Prof. Spiess for the special case of homonuclear 1H double-quantum spectroscopy. The generalization of these principles to the heteronuclear case is presented, with special emphasis on naturally abundant 13C-1H systems. For proton spectroscopy in the solid state, line-narrowing is of particular importance, and is here achieved by very-fast sample rotation at the magic angle (MAS), with frequencies up to 35 kHz. Therefore, the heteronuclear dipolar couplings are suppressed and have to be recoupled in order to achieve an efficient excitation of the observed multiple-quantum modes. Heteronuclear recoupling is most straightforwardly accomplished by performing the known REDOR experiment, where pi-pulses are applied every half rotor period. This experiment was modified by the insertion of an additional spectroscopic dimension, such that heteronuclear multiple-quantum experiments can be carried out, which, as shown experimentally and theoretically, closely resemble homonuclear double-quantum experiments. Variants are presented which are well-suited for the recording of high-resolution 13C-1H shift correlation and spinning-sideband spectra, by means of which spatial proximities and quantitative dipolar coupling constants, respectively, of heteronuclear spin pairs can be determined. Spectral editing of 13C spectra is shown to be feasible with these techniques. Moreover, order phenomena and dynamics in columnar mesophases with 13C in natural abundance were investigated. Two further modifications of the REDOR concept allow the correlation of 13C with quadrupolar nuclei, such as 2H. The spectroscopic handling of these nuclei is challenging in that they cover large frequency ranges, and with the new experiments it is shown how the excitation problem can be tackled or circumvented altogether, respectively. As an example, one of the techniques is used for the identification of a yet unknown motional process of the H-bonded protons in the crystalline parts of poly(vinyl alcohol).

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In this work, solid-state NMR methods suitable for the investigation of supramolecular systems were developed and improved. In this context, special interest was focussed on non-covalent interactions responsible for the formation of supramolecular structures, such as pi-pi interacions and hydrogen-bonds. In the first part of this work, solid-state NMR methods were presented that provide information on molecular structure and motion via the investigation of anisotropic interactions, namely quadrupole and dipole-dipole couplings, under magic-angle spinning conditions. A two-dimensional 2H double quantum experiment was developed, which is performed under off magic-angle conditions and correlates 2H isotropic chemical shifts with quasistatic DQ-filtered line shapes. From the latter, the quadrupole coupling parameters of samples deuterated at multiple sites can be extracted in a site-selective fashion. Furthermore, 7Li quadrupole parameters of lithium intercalated into TiO2 were determined by NMR experiments performed under static and MAS conditions, and could provide information on the crystal geometry. For the determination of 7Li-7Li dipole-dipole couplings, multiple-quantum NMR experiments were performed. The 1H-13C REREDOR experiment was found to be capable of determining strong proton-carbon dipole-dipole couplings with an accuracy of 500~Hz, corresponding to a determination of proton-carbon chemical-bond lengths with picometer accuracy In the second part of this work, solid-state NMR experiments were combined with quantum-chemical calculations in order to aid and optimise the interpretation of experimental results. The investigations on Calix[4]hydroquinone nanotubes have shown that this combined approach can provide information on the presence of disordered and/or mobile species in supramolecular structures. As a second example, C3-symmetric discs arranging in helical columnar stacks were investigated. In these systems, 1H chemical shifts experience large pi-shifts due to packing effects, which were found to be long-ranged. Moreover, quantum-chemical calculations revealed that helicity in these systems is induced by the propeller-like conformation of the core of the molecules.

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The goal of this thesis is the acceleration of numerical calculations of QCD observables, both at leading order and next–to–leading order in the coupling constant. In particular, the optimization of helicity and spin summation in the context of VEGAS Monte Carlo algorithms is investigated. In the literature, two such methods are mentioned but without detailed analyses. Only one of these methods can be used at next–to–leading order. This work presents a total of five different methods that replace the helicity sums with a Monte Carlo integration. This integration can be combined with the existing phase space integral, in the hope that this causes less overhead than the complete summation. For three of these methods, an extension to existing subtraction terms is developed which is required to enable next–to–leading order calculations. All methods are analyzed with respect to efficiency, accuracy, and ease of implementation before they are compared with each other. In this process, one method shows clear advantages in relation to all others.

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The Bedouin of South Sinai have been significantly affected by the politics of external powers for a long time. However, never had the interest of external powers in Sinai been so strong as since the Israeli-Egyptian wars in the second half of the 20th century when Bedouin interests started to collide with Egypt’s plans for a development of luxury tourism in South Sinai. rnrnThe tourism boom that has started in the 1980s has brought economic and infrastructure development to the Bedouin and tourism has become the most important source of income for the Bedouin. However, while the absolute increase of tourists to Sinai has trickled down to the Bedouin to some extent, the participation of Bedouin in the overall tourism development is under-proportionate. Moreover, the Bedouin have become increasingly dependent on monetary income and consequently from tourism as the only significant source of income while at the same time they have lost much of their land as well as their self-determination.rnrnIn this context, the Bedouin livelihoods have become very vulnerable due to repeated depressions in the tourism industry as well as marginalization. Major marginalization processes the Bedouin are facing are the loss of land, barriers to market entry, especially increasingly strict rules and regulations in the tourism industry, as well as discrimination by the authorities. Social differentiation and Bedouin preferences are identified as further factors in Bedouin marginalization.rnrnThe strategies Bedouin have developed in response to all these problems are coping strategies, which try to deal with the present problem at the individual level. Basically no strategies have been developed at the collective level that would aim to actively shape the Bedouin’s present and future. Collective action has been hampered by a variety of factors, such as the speed of the developments, the distribution of power or the decay of tribal structures.rnWhile some Bedouin might be able to continue their tourism activities, a large number of informal jobs will not be feasible anymore. The majority of the previously mostly self-employed Bedouin will probably be forced to work as day-laborers who will have lost much of their pride, dignity, sovereignty and freedom. Moreover, with a return to subsistence being impossible for the majority of the Bedouin, it is likely that an increasing number of marginalized Bedouin will turn to illegal income generating activities such as smuggling or drug cultivation. This in turn will lead to further repression and discrimination and could escalate in a serious violent conflict between the Bedouin and the government.rnrnDevelopment plans and projects should address the general lack of civil rights, local participation and protection of minorities in Egypt and promote Bedouin community development and the consideration of Bedouin interests in tourism development.rnrnWether the political upheavals and the resignation of president Mubarak at the beginning of 2011 will have a positive effect on the situation of the Bedouin remains to be seen.rn