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Collings JC Burke JM Smith PS Batsanov AS Howard JA Marder TB 《Organic & biomolecular chemistry》2004,2(21):3172-3178
A series of halogenated, partially fluorinated tolans of general formula p-X-C6H4-C[triple bond]C-C6F5[X=I (1), Br (2), Cl (3), F (4)] and p-X-C6F4-C[triple bond]C-C6H5[X=I (5), Br (6)] have been prepared via palladium-catalysed Sonogashira cross-coupling, or for X=Cl (7), by nucleophilic aromatic substitution reactions. The single-crystal X-ray structures of 1-3 and 5-6 have been determined. The structures reveal that the molecular packing is characterized by either arene-perfluoroarene interactions (3), or halogen-halogen interactions (isomorphous 1 and 2), or neither (isomorphous 5 and 6). The structure of represents the first fully determined crystal structure of a compound that contains a halogen atom other than fluorine, in which arene-perfluoroarene interactions are present. 相似文献
75.
Gil M. Barretto Peter J. Collings Dirk Bennemann Detlef Lötzsch Gerd Heppke 《Liquid crystals》2013,40(4):629-635
Optical activity measurements in the isotropic phase of two antiferroelectric liquid crystal systems in which the chirality can be varied reveal unusual behaviour of the short range order. In one system the phase sequence as the chirality is increased is smectic A, smectic C* A, and smectic Q. In the other system the phase sequence is smectic C*, smectic C* A, and smectic Q as the chirality is increased. The short range order of the isotropic phase behaves similarly for these systems, showing mean field behaviour at low chirality and far above the phase transition, but deviating from this behaviour significantly as the chirality is increased and the phase transition is approached. These optical activity results indicate how different is the short range order in the isotropic phase for these antiferroelectric liquid crystal systems and demonstrates the crucial role played by chirality. Past theoretical work that includes smecticlike fluctuations in the calculation of short range order in the isotropic phase is capable of qualitatively explaining these results. 相似文献
76.
Batsanov AS Collings JC Fairlamb IJ Holland JP Howard JA Lin Z Marder TB Parsons AC Ward RM Zhu J 《The Journal of organic chemistry》2005,70(2):703-706
Palladium-catalyzed terminal alkyne dimerization, through oxidative homocoupling, is a useful approach to the synthesis of symmetrical 1,4-diynes. Recent investigations have suggested that this reaction might be accomplished in the absence of intentionally added stoichiometric oxidants (to reoxidize Pd(0) to Pd(II)). In this paper, we have fully addressed the question of whether oxygen (or added oxidant) is required to facilitate this process. The presence of a stoichiometric quantity of air (or added oxidant such as I2) is essential for alkyne dimerization. Excess PPh3 inhibits alkyne dimerization to enyne, which only occurs to a significant extent when the reaction is starved of oxidant. Theoretical studies shed more light on the requirement for an oxidant in the homocoupling reaction in order for the process to be theromodynamically favorable. The employment of I2 as the stoichiometric oxidant appears to be the method of choice. The dual role of Cu both in transmetalation of alkynyl units to Pd(II) and in assisting reoxidation of Pd(0) to Pd(II) is suggested. 相似文献
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Recent theoretical work by numerous authors has indicated that pretransitional properties of the isotropic phase are highly dependent on the chirality of the nearby ordered phase. To test this aspect of the theories, we present results on the optical rotatory power in the isotropic phase for a series of four cholesteryl esters of varying chirality. The most important finding is that the separation between the first and second order transition temperatures decreases with an increase in chirality. However, the results of a recent experiment which claimed to present evidence for strong coupling between the structural modes of the ordered phase are not substantiated by the new measurements reported here. 相似文献
79.
Collings BA 《Journal of the American Society for Mass Spectrometry》2007,18(8):1459-1466
The efficiency of in-trap fragmentation in a low-pressure linear ion trap (LIT), using dipolar excitation, is dependent upon the choice of both the excitation q and the drive frequency of the quadrupole. In the work presented here, fragmentation efficiencies have been measured as a function of excitation q for drive frequencies of 816 kHz and 1.228 MHz. The experiments were carried out by fragmenting reserpine (609.23-->448.20 Th and 397.21-->365.19 Th transitions) and caffeine (195-->138 Th and 138-->110 Th transitions). The data showed that the onset of efficient fragmentation occurred at a lower Mathieu q for the LIT operated at 1.228 MHz when compared with the LIT operated at 816 kHz. A comparison of the fragmentation efficiency curves as a function of pseudo-potential well depth showed that the onset of fragmentation is independent of the drive frequency. In addition, a comparison of the fragmentation efficiency curves showed that all four of the precursor ions fragmented within a range of four V of pseudo-potential well depth. The choice of an appropriate excitation q can then be determined based upon a minimum pseudo-potential well depth, quadrupole field radius, drive frequency, and the mass of interest. Fragmentation efficiencies were also found to be significantly greater when using the higher drive frequency. 相似文献
80.
In the present work, the use of high power ultrasound as a process tool for the removal of persistent organic pollutants (POPs) from soil and the treatment of bauxite red mud waste from the Bayer process is discussed. Laboratory scale experiments have confirmed that the application of high power ultrasound to slurries of contaminated soil and of bauxite ore can treat two major environmental problems cost-effectively. Destruction rates of POPs in soil of 90% and higher have been achieved whereas 85% iron oxide has been extracted from red mud waste leaving a low-iron fraction of approximately 50% by weight which is more environmentally friendly.A 4 × 4 kW pilot plant capable of treating 2.5 tonnes of slurry per day has been commissioned to provide more accurate estimates of power and energy requirements to allow scale-up to industrial use. 相似文献