This review is an extensive update to the comprehensive review
on controlled/living radical polymerization (CLRP) in
dispersed systems published in 2008.

Controlled/Living Radical Polymerization in Dispersed Systems: An Update

Contemporary methods for dispersion of carbon nanotubes in water and non-aqueous media are discussed. Most attention is paid to ultrasonic and plasma techniques and other physical techniques, as well as to the use of surfactants, functionalizing and debundling agents of distinct nature (elemental substances, metal and organic salts, mineral and organic acids, oxides, inorganic and organic peroxides, organic sulfonates, polymers, dyes, natural products, biomolecules, and coordination compounds). Special studies on CNTs solubilization are examined.

Dispersion of carbon nanotubes in water and non-aqueous solvents

Fluorescent semiconductor nanocrystals (quantum dots) have the potential to revolutionize biological imaging, but their use has been limited by difficulties in obtaining nanocrystals that are biocompatible. To address this problem, we encapsulated individual nanocrystals in phospholipid block–copolymer micelles and demonstrated both in vitro and in vivo imaging. When conjugated to DNA, the nanocrystal-micelles acted as in vitro fluorescent probes to hybridize to specific complementary sequences. Moreover, when injected into Xenopus embryos, the nanocrystal-micelles were stable, nontoxic (<5 × 109 nanocrystals per cell), cell autonomous, and slow to photobleach. Nanocrystal fluorescence could be followed to the tadpole stage, allowing lineage-tracing experiments in embryogenesis.

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In vivo imaging with quantum dots encapsulated in phospholipid micelles

Carbon nanotubes (CNTs) have been proposed and actively explored as multipurpose innovative nanoscaffolds for applications in fields such as material science, drug delivery and diagnostic applications. Their versatile physicochemical features are nonetheless limited by their scarce solubilization in both aqueous and organic solvents. In order to overcome this drawback CNTs can be easily non-covalently functionalized with different dispersants. In the present review we focus on the peculiar hydrophobic character of pristine CNTs that prevent them to easily disperse in organic solvents. We report some interesting examples of CNTs dispersants with the aim to highlight the essential features a molecule should possess in order to act as a good carbon nanotube dispersant both in water and in organic solvents. The review pinpoints also a few examples of dispersant design. The last section is devoted to the exploitation of the major quality of non-covalent functionalization that is its reversibility and the possibility to obtain stimuli-responsive precipitation or dispersion of CNTs.

Non-covalent and reversible functionalization of carbon nanotubes

Nanocomposites composed of TiO2 and carbon materials (C) are widely popular photocatalysts because they combine the advantages of TiO2 (good UV photocatalytic activity, low cost, and stability) to the enhanced charge carrier separation and lower charge transfer resistance brought by carbon. However, the presence of carbon can also be detrimental to the photocatalytic performance as it can block the passage of light and prevent the reactant from accessing the TiO2 surface. Here using a novel interfacial in situ polymer encapsulation–graphitization method, where a glucose-containing polymer was grown directly on the surface of the TiO2, we have prepared uniform TiO2@C core–shell structures. The thickness of the carbon shell can be precisely and easily tuned between 0.5 and 8 nm by simply programming the polymer growth on TiO2. The resulting core@shell TiO2@C nanostructures are not black and they possess the highest activity for the photodegradation of organic compounds when the carbon shell thickness is 1–2...

TiO2@Carbon Photocatalysts: The Effect of Carbon Thickness on Catalysis.

A versatile encapsulation method of noncovalently modified carbon nanotubes by RAFT polymerization

Probing the carbon nanotube-surfactant interaction for the preparation of composites

Cadmium sulfide (CdS) quantum dots (QDs) encapsulated in block copolymer spheres were synthesized by an aqueous emulsion polymerization process. First, stable dispersions of CdS QDs in water were prepared using a polymer dispersant, either poly(acrylic acid) or a random copolymer having an average of ten acrylic acid and five butyl acrylate units. These polymer dispersants were prepared by reversible addition-fragmentation chain transfer polymerization. Then, the CdS QDs dispersed in water were encapsulated in a polystyrene shell using an emulsion polymerization process. Spectroscopic and microscopic techniques were used to characterize the resulting nanocomposites. Optical properties of QDs in polymer microspheres were investigated by UV-vis and fluorescence spectroscopic studies. Particle sizes of all CdS QD samples were calculated from absorption edges using Henglein's empirical curve. Transmission electron microscopy was used to determine the size and morphology of CdS QD samples. These observations were used to elucidate the mechanism of formation of the resulting well-defined polymer-encapsulated CdS nanoparticles.

Copolymer nanosphere encapsulated CdS quantum dots prepared by RAFT copolymerization: synthesis, characterization and mechanism of formation

Copolymers of 2-ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl-2-hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high-power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2-hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non-polar organic solvents, without altering the fundamental properties of the CNTs.

Supramolecular Complexes of Multivalent Cholesterol-Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents

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Weiheng Zhong

Papers

A versatile encapsulation method of noncovalently modified carbon nanotubes by RAFT polymerization

Probing the carbon nanotube-surfactant interaction for the preparation of composites

Copolymer nanosphere encapsulated CdS quantum dots prepared by RAFT copolymerization: synthesis, characterization and mechanism of formation

Supramolecular Complexes of Multivalent Cholesterol-Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents

PI-VAE: Physics-Informed Variational Auto-Encoder for stochastic differential equations