The aggregation kinetics of thermoresponsive core-shell micelles with a poly(N-isopropyl acrylamide) shell in pure water or in mixtures of water with the cosolvents methanol or ethanol at mole fractions of 5% is investigated during a temperature jump across the respective cloud point. Characteristically, these mixtures give rise to cononsolvency behavior. At the cloud point, aggregates are formed, and their growth is followed with time-resolved small-angle neutron scattering. Using the reversible association model, the interaction potential between the aggregates is determined from their growth rate in dependence on the cosolvents. The effect of the cosolvent is attributed to the interaction potential on the structured layer of hydration water around the aggregates. It is surmised that the latter is perturbed by the cosolvent and thus the residual repulsive hydration force between the aggregates is reduced. The larger the molar volume of the cosolvent, the more pronounced is the effect. This framework provides a molecular-level understanding of solvent-mediated effective interactions in polymer solutions and new opportunities for the rational control of self-assembly in complex soft matter systems.
FeCl(3) in combination with bisphosphine ligands represents an efficient catalyst system for the cross-coupling of aryl- and alkyl thiols with aryl iodides, a broad spectrum of functional groups can be tolerated during the catalysis.
We report here the iron-catalyzed cross-coupling reaction of alkyl vinyl halides with thiols. While many works are devoted to the coupling of thiols with alkyl vinyl iodides, interestingly, the known S-vinylation of vinyl bromides and chlorides is limited to 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene. Investigation on the coupling reaction of challenging alkyl vinyl bromides and chlorides with thiols is rare. Since the coupling of 1-(2-bromovinyl)benzene and 1-(2-chlorovinyl)benzene with thiols can be performed in the absence of any catalyst, here we focus on the coupling of thiols with alkyl vinyl halides. This system is generally reactive for alkyl vinyl iodides and bromides to provide the products in good yields. 1-(Chloromethylidene)-4-tert-butyl-cyclohexane was also coupled with thiols, giving the targets in moderate yields.
A copper-catalyzed cross-coupling reaction of alkynes with aryl iodides is described The system tolerates a broad range of functional groups and enables the use of sterically demanding substrates with only 1 0-2 5 mol-% of Cu(2)O and 1.0-2.5 mol-% of xantphos as the catalys
Back Cover: Adding a cosolvent to an aqueous solution of thermoresponsive micelles induces their aggregation. The growth rate is related to the interaction potential between the aggregates which changes due to the alteration of the hydration force by the cosolvent. This frame provides a molecular‐level understanding of solvent‐mediated effective interactions in polymer solutions. Further details can be found in the article by K. Kyriakos, M. Philipp, C.‐H. Lin, M. Dyakonova, N. Vishnevetskaya, I. Grillo, A. Zaccone, A. Miasnikova, A. Laschewsky, P. Müller‐Buschbaum, and C. M. Papadakis* on page 420.
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