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Core-crosslinked polymeric micelles (CCPMs) are an attractive class of nanocarriers for drug delivery. Two crosslinking approaches to form CCPMs exist: either via a low-molecular-weight crosslinking agent to connect homogeneous polymer chains with reactive handles or via cross-reactive handles on polymers to link them to each other (complementary polymers). Previously, CCPMs based on methoxy poly(ethylene glycol)- b-poly[ N-(2-hydroxypropyl) methacrylamide-lactate] (mPEG- b-PHPMAmLac n ) modified with thioesters were crosslinked via native chemical ligation (NCL, a reaction between a cysteine residue and thioester resulting in an amide bond) using a bifunctional cysteine containing crosslinker. These CCPMs are degradable under physiological conditions due to hydrolysis of the ester groups present in the crosslinks. The rapid onset of degradation observed previously, as measured by the light scattering intensity, questions the effectiveness of crosslinking via a bifunctional agent. Particularly due to the possibility of intrachain crosslinks that can occur using such a small crosslinker, we investigated the degradation mechanism of CCPMs generated via both approaches using various analytical techniques. CCPMs based on complementary polymers degraded slower at pH 7.4 and 37 °C than CCPMs with a crosslinker (the half-life of the light scattering intensity was approximately 170 h versus 80 h, respectively). Through comparative analysis of the degradation profiles of the two different CCPMs, we conclude that partially ineffective intrachain crosslinks are likely formed using the small crosslinker, which contributed to more rapid CCPM degradation. Overall, this study shows that the type of crosslinking approach can significantly affect degradation kinetics, and this should be taken into consideration when developing new degradable CCPM platforms.

In this paper, we report a new synthetic procedure to immobilize a transfer hydrogenation catalyst on the surface of colloidal polystyrene particles. Using supports of colloidal dimensions allows for combining a relatively high surface area for catalyst binding, mobility of the catalyst, and facile recovery by centrifugation or sedimentation. The immobilization procedure relies on the covalent attachment of terpyridine moieties on the particle surface. These immobilized terpyridines are subsequently employed as colloidal ligands, which participate in the formation of an active ruthenium-based transfer hydrogenation catalyst. The resulting functional colloidal particles successfully catalyze the transfer hydrogenation of acetophenone with 2-propanol as the hydrogen donor. Thorough analysis of the chemical composition of the colloidal surface led to the determination of the catalyst loading per particle. This enabled us to conduct reference hydrogenations with equal concentrations of the homogeneous transfer hydrogenation catalyst to probe the effect of the immobilization procedure on the catalytic activity. Despite a decrease in transfer hydrogenation activity, full acetophenone conversion is still achievable within 24 h. Preliminary experiments show that the catalytic colloids are recyclable without significant loss of transfer hydrogenation activity.

Chemically anisotropic dumbbell-shaped colloids are prepared starting from cross-linked polymer seed particles coated with a chlorinated outer layer. These chlorinated seeds are swollen with monomer. Subsequently, a liquid protrusion is formed on the surface of the seed particle by phase separation between the monomer and the swollen polymer network. Solidification of these liquid lobes by polymerization leads to the desired dumbbell-shaped colloids. The chlorine groups remain confined on the seed lobe of the particles, ensuring chemical anisotropy of the resulting particles. Exploiting the asymmetric distribution of the chemically reactive surface chlorine groups allows for site-specific surface modifications. Here we show that the geometry of the resulting chemically anisotropic dumbbells can be systematically tuned by a number of experimental parameters including the volume of styrene by which the seeds are swollen, the cross-link density of the chlorinated seeds and chemical composition/thickness of the chlorinated coating deposited on the seed particles. Being able to control the particle geometry, and therefore the Janus balance of these chemically anisotropic particles, provides a promising starting point for the synthesis of sophisticated building blocks for future (self-assembly) studies.

We report the preparation of chemically anisotropic colloidal dumbbells of which one lobe is functionalized with chemical handles in the form of chlorine groups. The chlorines are easily converted to azides and subsequently to active initiators for Atom Transfer Radical Polymerization (ATRP) by Click Chemistry. These initiators are exploited for site-specific grafting of poly(N-isopropylacrylamide) (p(NIPAM)) brushes on the reactive patches. The geometric ratio between the grafted and non-grafted lobe is tunable by the shape of the initial dumbbell and the polymer grafting time. Furthermore, the versatility of our synthesis protocol is underlined by extending it to colloids with multiple reactive patches. The partially grafted dumbbell-shaped particles are employed as building blocks for finite-sized colloidal clusters. A directional interaction between the non-grafted lobes is easily introduced by dispersing the partially grafted dumbbels in a high ionic strength medium. Finally, we briefly explore the potency of this system of forming stimuli-responsive colloidal clusters by exploiting the strongly temperature dependent properties of the grafted polymers.