A series of well-defined poly[(ethylene oxide)-block-2-(dimethylamino)ethyl methacrylate-block-2-(diethylamino) methacrylate] (PEO−DMA−DEA) triblocks were synthesized by successive ATRP polymerization of DMA and DEA monomers using PEO-based macroinitiators of different molecular weights. These triblock copolymers dissolved molecularly in aqueous solution at low pH; on addition of NaOH, micellization occurred at pH 7.1 to form three-layer “onionlike” micelles comprising DEA cores, DMA inner shells, and PEO coronas. Above pH 7.3, dynamic light scattering studies indicated unimodal, near-monodisperse populations, with mean micelle diameters of 27−84 nm depending on block compositions (for PEO113 triblock copolymers) and polydispersities typically less than 0.10. The average hydrodynamic diameter 〈D h〉 of the micelles decreased as the solution pH was increased from pH 7.3 to pH 9.0, indicating that the micelles become more compact due to deprotonation of the tertiary amine residues in the DMA and DEA blocks. 1H NMR studies supported a three-layer micelle structure and also revealed changes in the hydrophilicity of the DMA chains in the inner shell during cross-linking, which was achieved by adding the bifunctional alkyl iodide, 1,2-bis(2-iodoethoxy)ethane (BIEE). Selective quaternization of the DMA residues by the BIEE leads to increased hydrophilicity and colloid stability for the shell cross-linked (SCL) micelles. The minimum amount of BIEE required to “lock-in” the micellar structure depended on the thickness of the PEO corona:  shorter PEO chains led to enhanced cross-linking efficiency. At pH 8.5, the hydrodynamic diameter of un-cross-linked micelles increased rapidly above 40−50 °C due to the LCST behavior of the neutral DMA chains in the inner shell. In contrast, the dimensions of the SCL micelles in dilute aqueous solution are independent of temperature. These SCL micelles exhibit reversible swelling on varying the solution pH. At low pH, the DEA cores become protonated and hence hydrophilic. The effect of varying the block composition and the target degree of cross-linking on the structural stability and pH-dependent (de)swelling of the SCL micelles was systematically studied. Longer DEA blocks and lower target degrees of cross-linking led to increased swellability, as expected.

The homopolymerization and block/statistical copolymerization of 2-hydroxyethyl methacrylate (HEMA) using atom transfer radical polymerization (ATRP) in methanol at 20 °C has been investigated. For the homopolymerizations, both high conversions and low polydispersities (M w/M n < 1.25) were obtained over a wide range of target degrees of polymerization. According to the literature, HEMA homopolymer is usually described as only water-swellable, but in this work low molecular weight HEMA oligomers (target degrees of polymerization, DPn, less than 20) exhibited water solubility over a wide temperature range (no cloud point behavior). Furthermore, for actual DPn's between 20 and 45, HEMA homopolymers exhibited inverse temperature solubility in dilute aqueous solution at pH 6.5, and their cloud points increased systematically as the DPn was reduced. Gravimetric studies indicated that “water-insoluble” HEMA homopolymers with DPn's higher than 50 were actually partially soluble:  GPC studies confirmed that fractionation occurred due to preferential dissolution of the shorter chains. Furthermore, HEMA homopolymers with DPn's up to 50 are water-soluble at pH 2.2 and do not exhibit cloud points. This is attributed to protonation of the terminal morpholine groups derived from the ATRP initiator. Thus, depending on the mean DPn and the solution pH, water can be a good solvent, a marginal solvent or a nonsolvent for HEMA homopolymer. Chain extension (self-blocking) experiments conducted for the ATRP of HEMA in methanol at 20 °C using a Cu(I)Cl catalyst and bpy ligand indicated reasonable living character. Statistical copolymerizations of HEMA with other comonomers such as glycerol monomethacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA) allowed the cloud point behavior to be manipulated. Finally, a range of novel HEMA-based block copolymers were synthesized in which the HEMA block was either thermoresponsive or permanently hydrophilic, depending on its DPn and the nature of the second block. Thus, diblock copolymer micelles with either hydroxylated cores or coronas could be prepared.

Although several strategies are now available to produce functional microcompartments analogous to primitive cell-like structures, little progress has been made in generating protocell constructs with self-controlled membrane permeability. Here we describe the preparation of water-dispersible colloidosomes based on silica nanoparticles and delineated by a continuous semipermeable inorganic membrane capable of self-activated, electrostatically gated permeability. We use crosslinking and covalent grafting of a pH-responsive copolymer to generate an ultrathin elastic membrane that exhibits selective release and uptake of small molecules. This behaviour, which depends on the charge of the copolymer coronal layer, serves to trigger enzymatic dephosphorylation reactions specifically within the protocell aqueous interior. This system represents a step towards the design and construction of alternative types of artificial chemical cells and protocell models based on spontaneous processes of inorganic self-organization.

The homopolymerization of two hydroxy-functional monomers, glycerol monomethacrylate [GMA] and 2-hydroxypropyl methacrylate [HPMA], has been investigated using ATRP chemistry in aqueous, methanolic, or water/methanol solution. In methanol, both monomers are polymerized to high conversion with reasonably good control (final polydispersities are 1.30 and 1.09 for GMA and HPMA, respectively) within a few hours at 20 °C. “Self-blocking” chain growth experiments indicate good living character under these conditions. Addition of water leads to much more rapid polymerizations in both cases, but high polydispersities (e.g., M w/M n = 1.90 for a 50/50 water/methanol mixture) were always obtained with GMA. With HPMA, relatively low polydispersities (M w/M n = 1.17) can be achieved under the same conditions. Several new diblock copolymers were synthesized using poly(alkylene oxide)-based macroinitiators. One of these hydrophilic−hydrophobic diblocks proved to be thermoresponsive and aggregated reversibly in aqueous media.

Poly[(ethylene oxide)-block-glycerol monomethacrylate-block-2-(diethylamino)ethyl methacrylate] (PEO−GMA−DEA) and poly[(ethylene oxide)-block-2-hydroxyethyl methacrylate-block-2-(diethylamino)ethyl methacrylate] (PEO−HEMA−DEA) triblock copolymers were synthesized directly, without recourse to protecting group chemistry, via atom transfer radical polymerization by successive polymerization of GMA (or HEMA) and DEA monomers using a PEO-based macroinitiator. These triblock copolymers dissolved molecularly in aqueous solution at low pH; on addition of NaOH, micellization occurred above pH 7−8 to form three-layer “onionlike” micelles comprising DEA cores, GMA (or HEMA) inner shells, and PEO outer coronas. Selective cross-linking of the GMA (or HEMA) inner shell was successfully achieved by adding divinyl sulfone [DVS] to the alkaline micellar solution at room temperature. Unexpectedly, the PEO−HEMA−DEA triblock proved to be much less reactive toward DVS than the two PEO−GMA−DEA triblocks, and an excess of DVS was required to prepare shell cross-linked (SCL) micelles using the former triblock. The resulting SCL micelles exhibited reversible swelling behavior on varying the solution pH. At low pH, the DEA cores became protonated and hence hydrophilic. The effect of varying the block composition and the [DVS]/[GMA] molar ratio on the structural stability and pH-dependent (de)swelling of the SCL micelles was studied. Longer DEA blocks and lower [DVS]/[GMA] molar ratios led to increased swellability, as expected. Finally, these SCL micelles can serve as nanoreactors for the synthesis of gold nanoparticles. The basic DEA residues in the cores of the SCL micelles were first protonated using HAuCl4, and then the electrostatically bound AuCl4 - anions were reduced to nanoparticles of elemental gold using NaBH4 at neutral pH. The gold-loaded SCL micelles exhibited excellent long-term colloid stability.