Nonionic-zwitterionic diblock copolymers are designed to feature a coil-to-globule collapse transition with an upper critical solution temperature (UCST) in aqueous media, including physiological saline solution. The block copolymers that combine presumably highly biocompatible blocks are synthesized by chain extension of a poly(ethylene glycol) (PEG) macroinitiator via atom transfer radical polymerization (ATRP) of sulfobetaine and sulfabetaine methacrylates. Their thermoresponsive behavior is studied by variable temperature turbidimetry and 1 H NMR spectroscopy. While the polymers with polysulfobetaine blocks exhibit phase transitions in the physiologically interesting window of 30-50 • C only in pure aqueous solution, the polymers bearing polysulfabetaine blocks enabled phase transitions only in physiological saline solution. By copolymerizing a pair of structurally closely related sulfo-and sulfabetaine monomers, thermoresponsive behavior can be implemented in aqueous solutions of both low and high salinity. Surprisingly, the presence of the PEG blocks can affect the UCST-transitions of the polyzwitterions notably. In specific cases, this results in "schizophrenic" thermoresponsive behavior displaying simultaneously an UCST and an LCST (lower critical solution temperature) transition. Exploratory experiments on the UCST-transition triggered the encapsulation and release of various solvatochromic fluorescent dyes as model "cargos" failed, apparently due to the poor affinity even of charged organic compounds to the collapsed state of the polyzwitterions.
Smart, fully orthogonal switching was realized in a highly biocompatible diblock copolymer system with variable trigger-induced aqueous self-assembly. The polymers are composed of nonionic and zwitterionic blocks featuring lower and upper critical solution temperatures (LCSTs and UCSTs). In the system investigated, diblock copolymers from poly(Nisopropyl methacrylamide) (PNIPMAM) and a poly(sulfobetaine methacrylamide), systematic variation of the molar mass of the latter block allowed for shifting the UCST of the latter above the LCST of the PNIPMAM block in a salt-free condition. Thus, successive thermal switching results in "schizophrenic" micellization, in which the roles of the hydrophobic core block and the hydrophilic shell block are interchanged depending on the temperature. Furthermore, by virtue of the strong electrolyte-sensitivity of the zwitterionic polysulfobetaine block, we succeeded to shift its UCST below the LCST of the PNIPMAM block by adding small amounts of an electrolyte, thus inverting the pathway of switching. This superimposed orthogonal switching by electrolyte addition enabled us to control the switching scenarios between the two types of micelles (i) via an insoluble state, if the LCST-type cloud point is below the UCST-type cloud point, which is the case at low salt concentrations or (ii) via a molecularly dissolved state, if the LCST-type cloud point is above the UCST-type cloud point, which is the case at high salt concentrations. Systematic variation of the block lengths allowed for verifying the anticipated behavior and identifying the molecular architecture needed. The versatile and tunable self-assembly offers manifold opportunities, for example, for smart emulsifiers or for sophisticated carrier systems.
An investigation on the application of thermosensitive core−shell Fe 3 O 4 @PNIPAM nanogels in enhanced oil recovery was successfully performed. Here, the unique core−shell architecture was fabricated by conducting the polymerization at the surface of 3-butenoic acid-functionalized Fe 3 O 4 nanoparticles and characterized using X-ray diffraction (XRD), 1 H NMR, vibration sample magnetometer (VSM), and high-resolution transmission electron microscopy (HR-TEM). According to the results, this core−shell structure was beneficial for achieving the desired high viscosity and low nanofluid mobility ratio at high temperatures, which is essential for enhanced oil recovery (EOR) application. The results demonstrated that the nanogels exhibited a unique temperature-dependent flow behavior due to the PNIPAM shell's ability to transform from a hydrated to a dehydrated state above its low critical solution temperature (LCST). At such conditions, the nanogels exhibited a significantly low mobility ratio (M = 0.86), resulting in an even displacement front during EOR and leads to higher oil production. Based on the result obtained from sand pack flooding, about 25.75% of an additional secondary oil recovery could be produced when the nanofluid was injected at a temperature of 45 °C. However, a further increase in the flooding temperature could result in a slight reduction in oil recovery due to the precipitation of some of the severely aggregated nanogels at high temperatures.
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