- NMR-based molecular ruler for determining the depth of intercalants within the lipid bilayer. Part III: Studies on keto esters and acids
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The development of "molecular rulers" would allow one to quantitatively locate the penetration depth of intercalants within lipid bilayers. To this end, an attempt was made to correlate the 13C NMR chemical shift of polarizable "reporter" carbons (e.g., carbonyls) of intercalants within DMPC liposomal bilayers - with the polarity it experiences, and with its Angstrom distance from the interface. This requires families of molecules with two "reporter carbons" separated by a known distance, residing at various depths/polarities within the bilayer. For this purpose, two homologous series of dicarbonyl compounds, methyl n-oxooctadecanoates and the corresponding n-oxooctadecanoic acids (n = 4-16), were synthesized. To assist in assignment and detection several homologs in each system were prepared 13C-enriched in both carbonyls. Within each family, the number of carbons and functional groups remains the same, with the only difference being the location of the second ketone carbonyl along the fatty acid chain. Surprisingly, the head groups within each family are not anchored near the lipid-water interface, nor are they even all located at the same depth. Nevertheless, using an iterative best fit analysis of the data points enables one to obtain an exponential curve. The latter gives substantial insight into the correlation between polarity (measured in terms of the Reichardt polarity parameter, ET(30)) and penetration depth into the liposomal bilayer. Still missing from this curve are data points in the moderate polarity range.
- Afri, Michal,Alexenberg, Carmit,Aped, Pinchas,Bodner, Efrat,Cohen, Sarit,Ejgenburg, Michal,Eliyahu, Shlomi,Gilinsky-Sharon, Pessia,Harel, Yifat,Naqqash, Miriam E.,Porat, Hani,Ranz, Ayala,Frimer, Aryeh A.
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p. 105 - 118
(2015/02/19)
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- Effects of ligand exchange reactions on the composition of Cd1-yZnyTe grown by metalorganic vapor-phase epitaxy
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The metalorganic vapor-phase epitaxy (MOVPE) of cadmium zinc telluride (Cd1-yZnyTe) from dimethylcadmium (DMCd), dimethylzinc (DMZn), diethylzinc (DEZn), and diisopropyltelluride (DIPTe) was studied using on-line infrared spectroscopy to monitor the feed and effluent gases. The film composition was measured by X-ray diffraction. No zinc was incorporated into the film when DMCd and DMZn were used due to the very low reactivity of the latter compound. When DMCd and DEZn are tried, the films were nonuniform with Cd-rich films deposited at the reactor inlet and Zn-rich films deposited near the reactor outlet. This film profile was due to alkyl ligand exchange reactions between the group II precursors in the feed, producing DMZn, methylethylzinc (MEZn), methylethylcadmium (MECd), and diethylcadmium (DECd). The decomposition rates of these precursors vary over a wide range with DECd reacting at a 250 K lower temperature than DMZn. Since the organocadmium compounds were consumed at a much faster rate, CdTe was deposited first, while ZnTe was deposited downstream. The ligand exchange reactions explain why previous workers found it difficult to grow Cd1-yZnyTe alloys of uniform composition by MOVPE.
- Kappers, Menno J.,Wilkerson, Kerri J.,Hicks, Robert F.
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p. 4882 - 4888
(2007/10/03)
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