Redox-mediated synthesis and encapsulation of inorganic nanoparticles in shell-cross-linked cylindrical polyferrocenylsilane block copolymer micelles

Detailed studies of a new approach to the synthesis and encapsulation of silver and silver halide nanoparticles inside shell-cross-linked cylindrical block copolymer polyisoprene-block-polyferrocenyldimethylsilane (PI-b-PFS) micelles (1) through in situ redox reactions are reported. The cylindrical nanostructures 1 were prepared by the solution self-assembly of the PI-b-PFS diblock copolymer in the PI-selective solvent hexane followed by Pt(0)-catalyzed PI shell-cross-linking hydrosilylation reactions. The partial preoxidation of the swollen PFS core using tris(4-bromophenyl)aminium hexachloroantimonate [p-BrC6H4)3N][SbCl6] (2, Magic Blue) followed by redox reaction between the remaining Fe(II) centers in the PFS core and Ag(+) cations led to the formation of silver nanoparticles. High-resolution scanning transmission electron microscopy images of the resulting peapod structures provided a clear indication that the nanoparticles were encapsulated inside the micelles. The composition of the nanoparticles was analyzed by energy-dispersive X-ray spectroscopy (EDX). By combining the evolution of the UV-vis spectra of the reaction mixture and EDX measurements, we surprisingly found that silver halide seed particles were formed through a precipitation reaction at an early stage of the encapsulation process. The size of the silver nanoparticles varied with different amounts of silver ions added to the micelle solution. When I2 was used as the preoxidant, AgI nanoparticles were formed and encapsulated inside the cylinders through the precipitation reaction between iodide anions and silver ions. The packing density of the resulting AgI nanoparticles was increased by an iterative addition method, which utilizes the reversible redox properties of PFS. The small encapsulated AgI nanoparticles were also shown to serve as seeds for the formation of larger Ag nanoparticles when a silver salt was subsequently added.     

Simulation of block copolymer stabilized nanoparticles in a two-solvent system

In this paper, by using Brownian Dynamics simulation, we investigate in general terms the behavior of a nanoparticle stabilized by a block copolymer in the presence of an oil-water interface. We investigate the probability of sticking to the interface, the density distribution of the copolymer across the interface and the area occupied by the stabilized nanoparticle at the interface. By using representative snapshots of the stabilized nanoparticle, derived from the density distribution, we find that the nanoparticle stabilized by a block copolymer, with the hydrophobic side of it tethered to the nanoparticle, prefers sitting at the oil-phase, and thus has a contact angle that is tested to be larger than 90 degrees for most of the cases, even if the hydrophobe content is less than 50%. Thus we find the architecture of a block-copolymer attachment to have a significant effect on the emulsion type that would result.     

Amphiphilic block copolymer nanotubes and vesicles stabilized by photopolymerization

We report on a new method to stabilize nanotube and vesicle structures created from amphiphilic diblock copolymers by means of photopolymerization. Cross-linking with UV light exposure minimizes fluid disruption during stabilization. Additionally, the spatial control afforded by focusing or masking the initiating light source enables stabilization of distinct segments of individual nanostructures. This contribution demonstrates (1) that vesicles and nanotubes formed from poly(ethylene oxide)-block-polybutadiene are stabilized by exposure to UV light in the presence of a water-soluble photoinitiator and (2) that new nanotube geometries can be constructed by means of spot-curing, and (3) it reveals an application for photopolymerized nanotubes by showing electrophoresis of DNA through a UV-stabilized nanotube.     

Cross-linked block copolymer micelles: functional nanostructures of great potential and versatility

Supramolecular self assembly techniques have provided a versatile means by which to selectively assemble polymer molecules into well-defined three dimensional core-shell nanostructures. The covalent stabilisation and tailoring of these dynamic nanostructures can be achieved using a range of chemistries within the assembly to afford robust functional nanoparticles. Many examples of the stabilisation, functionalisation and decoration of these nanoparticles have been reported in the literature and this tutorial review will focus on these recent developments and highlight their potential applications.     

Cobalt nanoparticles in block copolymer micelles: Preparation and properties

 The preparation and properties of Co nanoparticles in polystyrene(PS)-poly-4-vinyl-py-ridine(PVP) micelles were studied. Elementary Co was generated by two methods: (i) by reduction of micelles loaded with CoCl₂, and (ii) by thermal decomposition of Co₂(CO)₈ in micel-lar solutions of such block copolymers. Co particles formed by both processes are effectively stabilized by the block copolymer matrix and do not aggregate. For CoCl₂ as a Co-source, the formed particles have a size less than 1 nm. Thermal treatment of such dried polymers at 200 ^°C for 2 h leads to spherical particles of 3–5 nm in size. The polymeric hybrid materials prepared in this way display remarkably high values of magnetization at rather low Co contents in the polymer, i.e., we obtain a tenfold increase of the specific magnetization density. Co₂(CO)₈ as a Co source, results in a more complex behavior. Co₂(CO)₈ dissolves in the solvent as well as in the micelle core where it is converted to an cationic–anionic complex involving the 4-VP units. The shape and size of the Co nanoparticles formed by thermolysis can be controlled by the balance of 4-VP/Co and can be varied from spherical particles in the limit of lower Co loads being mainly attached to the micelle core to a star-like and cubic morphology in case of excess of Co₂(CO)₈. Both superparamagnetic and ferromagnetic materials can be prepared. For ferromagnetic samples coercive force varies from 250 to 475 Oe depending on Co content and polymer sample. Received : 27 September 1996 Accepted: 22 November 1996     

Reversible pH-triggered encapsulation and release of pyrene by adsorbed block copolymer micelles

The well-established ability of copolymer micelles to encapsulate and release hydrophobic molecules has been investigated following their adsorption onto silica particles. Here, a pH-responsive copolymer, poly(2-(dimethylamino)ethyl methacrylate)- b-poly(2-(diethylamino)ethyl methacrylate) (PDMA(106)- b-PDEA(25)), has been used to study the formation and dissociation of adsorbed micelles through pH variation. This copolymer behaves as free unimers in aqueous solutions below pH 8 and forms micelles 29 nm in hydrodynamic diameter above this pH. Encapsulation and release of a model hydrophobic compound (pyrene) by in situ adjustment of the solution pH has been compared for both free and adsorbed micelles using fluorescence spectrophotometry, epifluorescence microscopy, and zeta potential measurements. At basic pH values, pyrene is solubilized within the cores of micelles adsorbed on silica particles: addition of acid leads to micelle dissociation and release of the pyrene into the bulk aqueous solution. Micelle adsorption does not appear to hinder the extent of pyrene uptake/release. Moreover, this pH-responsive behavior is both reversible and reproducible over multiple pH cycles.     

Self-assembly and chemical processing of block copolymers: A roadmap towards a diverse array of block copolymer nanostructures

Block copolymers can yield a diverse array of nanostructures.Their assembly structures are influenced by their inherent structures,and the wide variety of structures that can be prepared especially becomes apparent when one considers the number of routes available to prepare block copolymer assemblies.Some examples include self-assembly,directed assembly,coupling,as well as hierarchical assembly,which can yield assemblies having even higher structural order.These assembly routes can also be complemented by processing techniques such as selective crosslinking and etching,the former technique leading to permanent structures,the latter towards sculpted and the combination of the two towards permanent sculpted structures.The combination of these pathways provides extremely versatile routes towards an exciting variety of architectures.This review will attempt to highlight destinations reached by LIU Guojun and coworkers following these pathways.     

Covalent stabilization of nanostructures: Robust block copolymer templates from novel thermoreactive systems

Structurally robust block copolymer templates with feature sizes of approximately 10 nm were prepared from functionalized poly(methyl methacrylate)‐b‐polystyrene block copolymers. By the inclusion of benzocyclobutene crosslinking groups in the polystyrene block, the covalent stabilization of thin films to both thermal treatment and solvent exposure became possible. In addition, the crosslinking of the poly(styrene‐benzocyclobutene) domains at 220 °C, followed by the removal of poly(methyl methacrylate), provided a robust, crosslinked nanostructure with greater processing and fabrication potential. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1028–1037, 2005     

Grafting and patterned grafting of block copolymer nanotubes onto inorganic substrates

Chemical patterning of inorganic substrates by soft lithography has enabled various high-tech applications and cutting-edge fundamental research. In this paper, we report on methods for the grafting and patterned grafting of block copolymer nanotubes onto glass and mica surfaces. Under optimized conditions the density of such grafted nanotubes can be high, and most of the grafted tubes are in a standing position even after solvent evaporation. Surfaces modified with exotic reagents such as block copolymer nanofibers or nanotubes may find applications in biosensing, etc.     

Induction of periodic nanostructures in polythiophene films through block copolymer templating

A new class of periodically nanostructured polythiophene materials with high regularity and numerous morphologies is prepared through the cooperative self‐assembly of polythiophene derivatives with a templating block copolymer (BCP) and poly(1,4‐isoprene)‐block‐poly(methacrylic acid) (PMA). The selection of the hydrophilic and aprotic triethylene glycol (TEG) group as side chains on polythiophene and the use of hydrophilic and protic PMA are crucial to producing well‐ordered nanostructures in polythiophene films, as it enables selective coassembly within the hydrophilic domain through hydrogen bonding. The composite films are shown to have formed hexagonally packed cylinders with 28 nm periodicities based on small‐angle X‐ray scattering and transmission electron microscopy. The formation of hydrogen bonding is revealed by a shift in the carbonyl peak of PMA in the Fourier transform infrared spectra of the composite film relative to the neat film. This suggests that the TEG‐functionalized polythiophene selectively incorporates into PMA. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1105–1112     

Silica nanoparticle-loaded thermoresponsive block copolymer vesicles: a new post-polymerization encapsulation strategy and thermally triggered release

A thermoresponsive amphiphilic diblock copolymer that can form spheres, worms or vesicles in aqueous media at neutral pH by simply raising the dispersion temperature from 1 °C (spheres) to 25 °C (worms) to 50 °C (vesicles) is prepared via polymerization-induced self-assembly (PISA). Heating such an aqueous copolymer dispersion from 1 °C up to 50 °C in the presence of 19 nm glycerol-functionalized silica nanoparticles enables this remarkable ‘shape-shifting’ behavior to be exploited as a new post-polymerization encapsulation strategy. The silica-loaded vesicles formed at 50 °C are then crosslinked using a disulfide-based dihydrazide reagent. Such covalent stabilization enables the dispersion to be cooled to room temperature without loss of the vesicle morphology, thus aiding characterization and enabling the loading efficiency to be determined as a function of both copolymer and silica concentration. Small-angle X-ray scattering (SAXS) analysis indicated a mean vesicle membrane thickness of approximately 20 ± 2 nm for the linear vesicles and TEM studies confirmed encapsulation of the silica nanoparticles within these nano-objects. After removal of the non-encapsulated silica nanoparticles via multiple centrifugation–redispersion cycles, thermogravimetric analysis indicated that vesicle loading efficiencies of up to 86% can be achieved under optimized conditions. Thermally-triggered release of the silica nanoparticles is achieved by cleaving the disulfide bonds at 50 °C using tris(2-carboxyethyl)phosphine (TCEP), followed by cooling to 20 °C to induce vesicle dissociation. SAXS is also used to confirm the release of silica nanoparticles by monitoring the disappearance of the structure factor peak arising from silica–silica interactions.

A loading efficiency of up to 86% is achieved for silica nanoparticles encapsulated within crosslinkable redox-sensitive thermoresponsive diblock copolymer vesicles in water at 50 °C; triggered release is also demonstrated for this system.     

Using a liquid emulsion membrane system for the encapsulation of organic and inorganic substrates within inorganic microcapsules

We report the development of a novel technique for the encapsulation of molecular and condensed organic and inorganic substrates within hollow calcium carbonate microspheres; the process utilises precipitation at the oil-water interface of a pseudovesicular water-in-oil-in-water emulsion liquid membrane (ELM) system in order to create an inorganic shell around the pre-dispersed media.     

Phosphorus-containing block copolymer templates can control the size and shape of gold nanostructures

Amphiphilic block copolymers containing phosphine moieties in the main chain are employed as macromolecular ligands for gold(I). The sequential living anionic copolymerization of isoprene (I) and the phosphaalkene, MesP CPh2 (Mes = 2,4,6-trimethylphenyl) affords the block copolymer [PI]404-b-[MesP-CPh2]32 (1a). The incorporation of gold(I) moieties into this functional copolymer is accomplished by treating 1 with THT.AuCl (THT = tetrahydrothiophene) which affords [PI]404-b-[MesP(AuCl)-CPh2]32 (2a). Remarkably, dissolution of gold-functionalized 2 in n-heptane, a block-selective solvent for isoprene, affords spherical micelles with gold(I)-rich cores. Micelles were examined by transmission electron microscopy (TEM) and dynamic light scattering (DLS). We also prepared two additional copolymers with longer phosphine blocks and shorter PI segments: [PI]222-b-[MesP(AuCl)-CPh2]77 (2b) and [PI]164-b-[MesP(AuCl)-CPh2]85 (2c). When assembled in isoprene-selective solvents, 2b forms wormlike structures and 2c, with the longest phosphine block, forms fascinating micron sized intertwined wormlike structures. This represents a new method to control the shape and size of gold(I) nanostructures.     

Novel supramolecular block copolymer containing organic–inorganic pentablock copolymer by ATRP of styrene and vinyl acetate using polydimethylsiloxane/cyclodextrin inclusion complexes as macroinitiator

Organic–inorganic pentablock copolymers have been synthesized via atom transfer radical polymerization (ATRP) of styrene (St) and vinyl acetate (VAc) monomers at 60 °C using CuCl/N,N,N′,N″,N″-pentamethyldiethylenetriamine as a catalyst system initiated from boromoalkyl-terminated poly(dimethylsiloxane) (PDMS)/cyclodextrins macroinitiator (Br-PDMS/γ-CD). Br-PDMS-Br was reacted with γ-CD in different conditions with inclusion complexes being characterized through hydrogen nuclear magnetic resonance (¹H NMR) and differential scanning calorimetry (DSC). Resulting Br-PDMS-Br/γ-CD inclusion complexes were taken as macroinitiators for ATRP of St and VAc. Well-defined poly(styrene)-b-poly(vinyl acetate)-b-poly(dimethylsiloxane/γ-cyclodextrin)-b-poly(vinyl acetate)-b-poly(styrene) (PSt-b-PVAc-b-PDMS/γ-CD-b-PVAc-b-PSt) pentablock copolymer was characterized by ¹H NMR, gel permeation chromatograph (GPC) and DSC. There was a good agreement between the number-average molecular weight calculated from ¹H NMR spectra and that of theoretically calculated. Pentablock copolymers consisting of Br-PDMS-Br/γ-CD inclusion complex as central blocks (inorganic block) and PVAc and PSt as terminal blocks were synthesized by this technique. PSt-b-PVAc-b-PDMS/γ-CD-b-PVAc-b-PSt pentablock copolymer can undergo a temperature-induced reversible transition upon heating of the copolymer complex from white complex at 22 °C to green complex in 55 °C which characterized with XRD and ¹H NMR. XRD showed a change in crystallinity percent of St peak with changing the temperature which calculated by Origin75 software.     

Ionic liquids for the convenient synthesis of functional nanoparticles and other inorganic nanostructures

Ionic liquids are a new class of organic solvents with high polarity and a preorganized solvent structure. Very polar reactions can be carried out in these liquid in the absence of or with a controlled amount of water, and crystalline nanoparticles can be synthesized conveniently at ambient temperatures. The pronounced self-organization of the solvent is used in the synthesis of self-assembled, highly organized hybrid nanostructures with unparalleled quality. The extraordinary potential of ionic liquids in materials synthesis is described in this minireview and a physicochemical explanation is given.     

Aggregation behavior of pH- and thermo-responsive block copolymer protected gold nanoparticles

Two distinctive block copolymers protected gold nanoparticles (AuNPs) were prepared with poly(methylacrylic acid)-block-poly(N-isopropylacrylamide) (SH-PMAA₆₄-b-PNIPAM₃₅) and poly (N-isopropylacrylamide)-block-poly(methylacrylic acid) (SH-PNIPAM₄₀-b- PMAA₆₀) through strong gold-sulfur bonding. The hybrid NPs have a pH-responsive inner shell (or corona) and a thermo-responsive corona (or inner shell) due to different location relations of the PNIPAM and PMAA on the surface of AuNPs. Then, the aggregation behaviors, as well as the changes of optical properties, of two hybrid NPs were compared in response to both stimuli. The results showed the obvious inter-particle aggregation caused by the phase transition for hydrophobic coronal polymer. However, the particles of hydrophilic corona layer retained good dispersion and the pH-responsive or thermo-responsive characteristics of shell layer made relatively minor changes.     

Synthesis of sodium-polystyrenesulfonate-grafted nanoparticles by core-cross-linking of block copolymer micelles

Sodium poly(styrenesulfonate)(polySSNa)-grafted polymer nanoparticles were synthesized by core-cross-linking of block copolymer micelles and subsequent chemical transformation. Block copolymers, poly(p-((1-methyl)silacyclobutyl)styrene-block-poly(neopentyl p-styrenesulfonate)s, polySBS-b-polySSPen, were synthesized by nitroxy-mediated living radical polymerization. The block copolymers formed micelles (R_h=15-23 nm, where R_h represents the hydrodynamic radius) with a polySBS core and polySSPen shell in acetone. The micelle core was cross-linked by ring-opening polymerization of silacyclobutyl groups in polySBS. Hydrolysis of the neopentyl groups provided polySSNa-grafted nanoparticles. The R_h of the particles before the hydrolysis ranged from 12 to 21 nm in acetone, while they varied to the range from 50 to 110 nm in water after the hydrolysis.     

Near-infrared light-triggered dissociation of block copolymer micelles using upconverting nanoparticles

We demonstrate a novel strategy enabling the use of a continuous-wave diode near-infrared (NIR) laser to disrupt block copolymer (BCP) micelles and trigger the release of their "payloads". By encapsulating NaYF(4):TmYb upconverting nanoparticles (UCNPs) inside micelles of poly(ethylene oxide)-block-poly(4,5-dimethoxy-2-nitrobenzyl methacrylate) and exposing the micellar solution to 980 nm light, photons in the UV region are emitted by the UCNPs, which in turn are absorbed by o-nitrobenzyl groups on the micelle core-forming block, activating the photocleavage reaction and leading to the dissociation of BCP micelles and release of co-loaded hydrophobic species. Our strategy of using UCNPs as an internal UV or visible light source upon NIR light excitation represents a general and efficient method to circumvent the need for UV or visible light excitation that is a common drawback for light-responsive polymeric systems developed for potential biomedical applications.