Temperature effects upon aqueous micellar-assisted decarboxylation of 6-nitrobenzisoxazole-3-carboxylate and its 5-methyl derivative.
An investigation of temperature effects upon first-order rate constants in the micellar pseudophase for decarboxylation of 6-nitrobenzisoxazole-3-carboxylate (6-NBIC) and its 5-methyl derivative (6-NBIC-5-Me) was carried out. Surfactants used were cationic cetyltrialkylammonium bromide with alkyl = methyl (CTABr), ethyl (CTEABr), n-propyl (CTPABr), and n-butyl (CTBABr). The investigation shows that micelles speed up reactions by decreasing enthalpies of activation. Increase in head group bulk further speeds reactions still by a small decrease in the enthalpies, for both substrates. Values of DeltaH# and DeltaS# for 6-NBIC in the various surfactants give linear isokinetic plot, with CTBABr as outlier.
Dielectric relaxation spectroscopy shows a sparingly hydrated interface and low counterion mobility in triflate micelles.
The properties of ionic micelles are affected by the nature of the counterion. Specific ion effects can be dramatic, inducing even shape and phase changes in micellar solutions, transitions apparently related to micellar hydration and counterion binding at the micellar interface. Thus, determining the hydration and dynamics of ions in micellar systems capable of undergoing such transitions is a crucial step in understanding shape and phase changes. For cationic micelles, such transitions are common with large organic anions as counterions. Interestingly, however, phase separation also occurs for dodecyltrimethylammonium triflate (DTATf) micelles in the presence of sodium triflate (NaTf). Specific ion effects for micellar solutions of dodecyltrimethylammonium chloride (DTAC), bromide (DTAB), methanesulfonate (DTAMs), and triflate (DTATf) were studied with dielectric relaxation spectroscopy (DRS), a technique capable of monitoring hydration and counterion dynamics of micellar aggregates. In comparison to DTAB, DTAC, and DTAMs, DTATf micelles were found to be considerably less hydrated and showed reduced counterion mobility at the micellar interface. The obtained DTATf and DTAMs data support the reported central role of the anion's -CF3 moiety with respect to the properties of DTATf micelles. The reduced hydration observed for DTATf micelles was rationalized in terms of the higher packing of this surfactant compared to that of other DTA-based systems. The decreased mobility of Tf(-) anions condensed at the DTATf interface strongly suggests the insertion of Tf(-) in the micellar interface, which is apparently driven by the strong hydrophobicity of -CF3.
Keeping Farmers on the Land: Adding Value in Agriculture in the Veneto Region of Italy
Italy's relatively small area, high population density, and high land and labor costs have created the challenges of ensuring profitably for agricultural producers, slowing urban encroachment onto arable land, and keeping farm families on land that has been handed down within the families for generations. As part of the solution to these issues, the European Union is enacting policies to reduce producer dependence on direct subsidies while increasing the competitiveness of agricultural products and returns to producers, reinvigorating rural communities, and encouraging environmentally sound production methods. These regulations provide incentives for producers to add value to their products by obtaining legal recognition of typical products, participating in agritourism, and helping to promote traditional products for regional food systems. This paper examines how E.U. and national policies are encouraging farmers in the Veneto region of Italy to adopt an agricultural production model that encourages limited production of high-quality, high-value products and more diversified land use.