Organic–inorganic hybrid nanomaterials prepared <i>via</i> polymerization-induced self-assembly: recent developments and future opportunities

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Abstract

This review highlights recent developments in the preparation of organic–inorganic hybrid nanomaterials via polymerization-induced self-assembly.

Abstract

Organic–inorganic hybrid nanomaterials are an important class of functional materials that find applications in many areas. Cooperative self-assembly of inorganic nanoparticles and block copolymers in solution is one of the most widely employed approaches for preparing organic–inorganic hybrid nanomaterials with precise structures and properties. However, this method usually encounters problems with low solids contents (<1% w/w) and multi-step processes, and is difficult to implement on a large scale. Over the past decade or so, the development of polymerization-induced self-assembly (PISA) has enabled the preparation of concentrated block copolymer nanomaterials (10–50% w/w solids) with a diverse set of morphologies. This review focuses on recent developments in the preparation of organic–inorganic hybrid nanomaterials via PISA including: (i) post-modification of block copolymer nanoparticles, (ii) in situ encapsulation of inorganic nanoparticles into vesicles, (iii) cooperative self-assembly of inorganic nanoparticles and polymers. By highlighting these important developments, the current challenges and future opportunities of organic–inorganic hybrid nanomaterials prepared via PISA are also provided.

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Nanoparticle-Based Medicines: A Review of FDA-Approved Materials and Clinical Trials to Date

Daniel Bobo, Kye J. Robinson, Jiaul Islam … (2016)

In this review we provide an up to date snapshot of nanomedicines either currently approved by the US FDA, or in the FDA clinical trials process. We define nanomedicines as therapeutic or imaging agents which comprise a nanoparticle in order to control the biodistribution, enhance the efficacy, or otherwise reduce toxicity of a drug or biologic. We identified 51 FDA-approved nanomedicines that met this definition and 77 products in clinical trials, with ~40% of trials listed in clinicaltrials.gov started in 2014 or 2015. While FDA approved materials are heavily weighted to polymeric, liposomal, and nanocrystal formulations, there is a trend towards the development of more complex materials comprising micelles, protein-based NPs, and also the emergence of a variety of inorganic and metallic particles in clinical trials. We then provide an overview of the different material categories represented in our search, highlighting nanomedicines that have either been recently approved, or are already in clinical trials. We conclude with some comments on future perspectives for nanomedicines, which we expect to include more actively-targeted materials, multi-functional materials ("theranostics") and more complicated materials that blur the boundaries of traditional material categories. A key challenge for researchers, industry, and regulators is how to classify new materials and what additional testing (e.g. safety and toxicity) is required before products become available.

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Polymerization-Induced Self-Assembly of Block Copolymer Nano-objects via RAFT Aqueous Dispersion Polymerization

Nicholas Warren, Steven Armes (2014)

In this Perspective, we discuss the recent development of polymerization-induced self-assembly mediated by reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization. This approach has quickly become a powerful and versatile technique for the synthesis of a wide range of bespoke organic diblock copolymer nano-objects of controllable size, morphology, and surface functionality. Given its potential scalability, such environmentally-friendly formulations are expected to offer many potential applications, such as novel Pickering emulsifiers, efficient microencapsulation vehicles, and sterilizable thermo-responsive hydrogels for the cost-effective long-term storage of mammalian cells.

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Mechanistic insights for block copolymer morphologies: how do worms form vesicles?

Adam Blanazs, Jeppe Madsen, Giuseppe Battaglia … (2011)

Amphiphilic diblock copolymers composed of two covalently linked, chemically distinct chains can be considered to be biological mimics of cell membrane-forming lipid molecules, but with typically more than an order of magnitude increase in molecular weight. These macromolecular amphiphiles are known to form a wide range of nanostructures (spheres, worms, vesicles, etc.) in solvents that are selective for one of the blocks. However, such self-assembly is usually limited to dilute copolymer solutions ( 99% monomer conversion) at relatively high solids in purely aqueous solution. Furthermore, careful monitoring of the in situ polymerization by transmission electron microscopy reveals various novel intermediate structures (including branched worms, partially coalesced worms, nascent bilayers, "octopi", "jellyfish", and finally pure vesicles) that provide important mechanistic insights regarding the evolution of the particle morphology during the sphere-to-worm and worm-to-vesicle transitions. This environmentally benign approach (which involves no toxic solvents, is conducted at relatively high solids, and requires no additional processing) is readily amenable to industrial scale-up, since it is based on commercially available starting materials.