In this review we will focus on how magnetic fields can be used to manipulate the motion of various micro- and nanostructures in solution. We will distinguish between ferromagnetic, paramagnetic and diamagnetic materials. Furthermore, the use of various kinds of magnetic fields, such as homogeneous, inhomogeneous and rotating magnetic fields, is discussed. To date most research has focused on the use of ferro- and paramagnetic materials, but here we also describe the possibilities of magnetic manipulation of diamagnetic materials. Since the vast majority of soft matter is diamagnetic, this paves the way for many new applications to manipulate the motion of micro- and nanostructures.

Polymersomes are robust, versatile nanostructures that can be tailored by varying the chemical structure of copolymeric building blocks, giving control over their size, shape, surface chemistry, and membrane permeability. In particular, the generation of nonspherical nanostructures has attracted much attention recently, as it has been demonstrated that shape affects function in a biomedical context. Until now, nonspherical polymersomes have only been constructed from nondegradable building blocks, hampering a detailed investigation of shape effects in nanomedicine for this category of nanostructures. Herein, we demonstrate the spontaneous elongation of spherical polymersomes comprising the biodegradable copolymer poly(ethylene glycol)-b-poly(d,l-lactide) into well-defined nanotubes. The size of these tubes is osmotically controlled using dialysis, which makes them very easy to prepare. To confirm their utility for biomedical applications, we have demonstrated that, alongside drug loading, functional proteins can be tethered to the surface utilizing bio-orthogonal “click” chemistry. In this way the present findings establish a novel platform for the creation of biocompatible, high-aspect ratio nanoparticles for biomedical research.

Polymersomes are bilayer vesicles, self-assembled from amphiphilic block copolymers. They are versatile nanocapsules with adjustable properties, such as flexibility, permeability, size and functionality. However, so far no methodological approach to control their shape exists. Here we demonstrate a mechanistically fully understood procedure to precisely control polymersome shape via an out-of-equilibrium process. Carefully selecting osmotic pressure and permeability initiates controlled deflation, resulting in transient capsule shapes, followed by reinflation of the polymersomes. The shape transformation towards stomatocytes, bowl-shaped vesicles, was probed with magnetic birefringence, permitting us to stop the process at any intermediate shape in the phase diagram. Quantitative electron microscopy analysis of the different morphologies reveals that this shape transformation proceeds via a long-predicted hysteretic deflation–inflation trajectory, which can be understood in terms of bending energy. Because of the high degree of controllability and predictability, this study provides the design rules for accessing polymersomes with all possible different shapes.

Stomatocytes are polymersomes with an infolded bowl-shaped architecture. This internal cavity is connected to the outside environment via a small ‘mouth’ region. Stomatocytes are assembled from diamagnetic amphiphilic block-copolymers with a highly anisotropic magnetic susceptibility, which permits to magnetically align and deform the polymeric self-assemblies. Here we show the reversible opening and closing of the mouth region of stomatocytes in homogeneous magnetic fields. The control over the size of the opening yields magneto-responsive supramolecular valves that are able to reversibly capture and release cargo. Furthermore, the increase in the size of the opening is gradual and starts at fields below 10 T, which opens the possibility of using these structures for delivery and nanoreactor applications.

Magnetic birefringence was used for in situ monitoring of the morphological changes in diamagnetic polymersomes during shape-transformation by dialysis. The birefringence was found to be very sensitive to the polymersome morphology, as determined by electron microscopy. The deflation of polymersomes into disks was observed, followed by a bending and partial inflation into stomatocytes.

Accurate control of the shape transformation of polymersome is an important and interesting challenge that spans across disciplines such as nanomedicine and nanomachine. Here, we report a fast and facile methodology of shape manipulation of polymersome via out-of-equilibrium polymer self-assembly and shape change by chemical addition of additives. Due to its increased permeability, hydrophilicity, and fusogenic properties, poly(ethylene oxide) was selected as the additive for bringing the system out of equilibrium via fast addition into the polymersome organic solution. A new shape, stomatocyte-in-stomatocyte (sto-in-sto), is obtained for the first time. Moreover, fast shape transformation within less than 1 min to other relevant shapes such as stomatocyte and large compound vesicles was also obtained and accurately controlled in a uniform dispersion. This methodology is demonstrated as a general strategy with which to push the assembly further out of equilibrium to generate unusual nanostructures in a controllable and fast manner.

Polymersomes, vesicles self-assembled from amphiphilic block copolymers, are well known for their robustness and for their broad applicability. Generating polymersomes of different shape is a topic of recent attention, specifically in the field of biomedical applications. To obtain information about their exact shape, tomography based on cryo-electron microscopy is usually the most preferred technique. Unfortunately, this technique is rather time consuming and expensive. Here we demonstrate an alternative analytical approach for the characterization of differently shaped polymersomes such as spheres, prolates and discs via the combination of multi-angle light scattering (MALS) and quasi-elastic light scattering (QELS). The use of these coupled techniques allowed for accurate determination of both the radius of gyration (R g ) and the hydrodynamic radius (R h ). This afforded us to determine the shape ratio ρ (R g /R h ) with which we were able to distinguish between polymersome spheres, discs and rods.

Manipulation of Micro-and Nanostructure Motion with Magnetic Fields -[117 refs.]. -(RIKKEN, R. S. M.; NOLTE, R. J. M.; MAAN, J. C.; VAN HEST, J. C. M.; WILSON, D. A.; CHRISTIANEN, P. C. M.; Soft Matter 10 (2014) 9, 1295-1308, http://dx.doi.org/10.1039/c3sm52294f ; High Field Magn. Lab., Radboud Univ. Nijmegen, NL-6525 ED Nijmegen, Neth.; Eng.) -Schramke 16-280