Nanostructuration of self-assembled poly(styrene-b-isoprene-b-styrene) block copolymer thin films in a highly oriented pyrolytic graphite substrate

Highly oriented pyrolitic graphite (HOPG) is a useful substrate to visualize epitaxial formation due to its crystallographic structure. The morphology of a poly(styrene-b-isoprene-b-styrene) block copolymer thin film on a HOPG substrate was investigated by atomic force microscopy. Block copolymer domains generated a morphology with triangular regularity. This arrangement was induced by the HOPG substrate structure due to van der Waals attraction between the HOPG π-conjugated system and aromatic ring of polystyrene domains. However, increasing the film thickness, the substrate effect on the surface morphology decreased. As a consequence, film surfaces showed the coexistence of different structures such as highly aligned cylinders and perforated lamellae. When film thickness exceeded a threshold value, the substrate did not have effect in the surface arrangements and the surface showed a similar morphology to that existing in bulk.     

Nanostructured physical gel of SBS block copolymer and Ag/DT/SBS nanocomposites

Thermoreversible physical gels of poly(styrene-b-butadiene-b-styrene) (SBS), formed by the dissolution of the block copolymer in a mid-block-selective solvent (THF), have been studied and characterized with particular attention to their morphology and rheological behavior. The effects of the addition of silver (Ag) nanoparticles to the SBS matrix, on the behavior of the physical gels, were also studied. The external surface of the Ag nanoparticles has been modified by using as surfactant material, dodecanethiol, in order to achieve their confinement in just one block of the SBS block copolymer matrix. The results of this study show that the gel stability is not affected by the presence of Ag nanoparticles. In fact, the micellar domains of the nanocomposite gel based on SBS block copolymer and Ag nanoparticles has been obtained and the physical gel behavior have been confirmed by rheological analysis.     

Self-assembled monolayer-modified block copolymers for chemical surface nanopatterning

Thin-film poly(styrene-block-methyl methacrylate) diblock copolymer (PS-b-PMMA) is used to create chemically patterned surfaces via metal deposition combined with self-assembled monolayers (SAMs) and UV exposure. We use this method to produce surfaces that are chemically striped on the scale of a few tens of nanometers. Atomic force and transmission electron microscopies are used to verify the spatially localized organization of materials, and contact angle measurements confirm the chemical tunability of these scaffolds. These surfaces may be used for arraying nanoscale objects, such as nanoparticles or biological species, or for electronic, magnetic memory or photovoltaic applications.     

Engineering of poly(ethylene glycol) chain-tethered surfaces to obtain high-performance bionanoparticles

Abstract

A poly(ethylene glycol)-b-poly[2-(N,N-dimethylamino)ethyl methacrylate] block copolymer possessing a reactive acetal group at the end of the poly(ethylene glycol) (PEG) chain, that is, acetal-PEG-b-PAMA, was synthesized by a proprietary polymerization technique. Gold nanoparticles (GNPs) were prepared using the thus-synthesized acetal-PEG-b-PAMA block copolymer. The PEG-b-PAMA not only acted as a reducing agent of aurate ions but also attached to the nanoparticle surface. The GNPs obtained had controlled sizes and narrow size distributions. They also showed high dispersion stability owing to the presence of PEG tethering chains on the surface. The same strategy should also be applicable to the fabrication of semiconductor quantum dots and inorganic porous nanoparticles. The preparation of nanoparticles in situ, i.e. in the presence of acetal-PEG-b-PAMA, gave the most densely packed polymer layer on the nanoparticle surface; this was not observed when coating preformed nanoparticles. PEG/polyamine block copolymer was more functional on the metal surface than PEG/polyamine graft copolymer, as confirmed by angle-dependent x-ray photoelectron spectroscopy. We successfully solubilized the C₆₀ fullerene into aqueous media using acetal-PEG-b-PAMA. A C₆₀/acetal-PEG-b-PAMA complex with a size below 5 nm was obtained by dialysis. The preparation and characterization of these materials are described in this review.     

Two Dimensional Nanoarrays of Individual Protein Molecules

Protein molecules on solid surfaces are essential to a number of applications, such as biosensors, biomaterials, and drug delivery. In most approaches for protein immobilization, inter‐molecular distances on the solid surface are not controlled and this may lead to aggregation and crowding. Here, a simple approach to immobilize individual protein molecules in a well‐ordered 2D array is shown, using nanopatterns obtained from a polystyrene‐block‐poly(2‐hydroxyethyl methacrylate) (PS‐b‐PHEMA) diblock copolymer thin film. This water‐stable and protein‐resistant polymer film contains hexagonally ordered PS cylindrical domains in a PHEMA matrix. The PS domains are activated by incorporating alkyne‐functionalized PS and immobilizing azide‐tagged proteins specifically onto each PS domain using “Click” chemistry. The nanometer size of the PS domain dictates that each domain can accommodate no more than one protein molecule, as verified by atomic force microscopy imaging. Immunoassay shows that the amount of specifically bound antibody scales with the number density of individual protein molecules on the 2D nanoarrays.     

H-bonding driven assembly of colloidal Au nanoparticles on nanostructured poly(styrene-b-ethylene oxide) block copolymer templates

A facile, cost-effective, and general solution-based “bottom-up” method for nanopatterning dense arrays of colloidal Au nanoparticles (NPs) has been developed. The organization of the NPs has been successfully achieved onto a microphase-separated poly(styrene-block-ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin film which acts as structural template. The NP assembly process occurs by incubating the BCP films in dispersions of the ex situ synthesized Au NPs, not requiring any chemical pre-treatment or activation step of the copolymer surface, and has demonstrated to be distinctively controlled by multiple, cooperative, and selective hydrogen bonding interactions between hydroxyl functionalities of the capping molecules coating the Au NP surface and the hydrophilic PEO block. The effect of incubation time and concentration of NPs on the selectivity of the assembly has been investigated by atomic force and scanning electron microscopy. The results show that the BCP pattern is preserved after decoration with the Au NPs. The fabricated nanopatterns are good candidates for nanostructure integration in sensing and optoelectronic applications, as well as in memory devices and photonic systems. Moreover, the proposed immobilization protocol represents a model system that can be extended to other NPs having different compositions and surface chemistries.     

SAXS observation of RCM1 under cyclical shear

A cylinder forming poly(styrene-b-butadiene-b-styrene) triblock copolymer melt is cyclically processed through a capillary at a high shear rate in the Cambridge Multipass Rheometer (MPR). In situ X-ray diffraction experiments enable observation of the effect of the shear on the block copolymer (BCP) nanophase orientation, both during and after processing. Temporal resolution of the X-ray exposures is increased, whilst retaining intensity, by exploiting the cyclical nature of the shear and the material’s response to it; short exposures from many cycles, individually having few counts, are added together to produce well resolved X-ray patterns. Orientation of the cylinders reduces during processing, then increases during pauses between processing. The loss of orientation is attributed to the high shear rate deforming the melt faster than the structure can respond, whilst it is believed that melt relaxation, linked to the compressibility of the material, produces much lower shear rates after mechanical processing has ceased, which induces strong orientation of the nanostructure.     

Formation of Ag nanoparticles within the thermosensitive hairy hybrid particles

Herein we report on the production of composite core-shell particles, which are actually self-assembly of poly (N-isopropylacrylamide)-based amphiphilic block copolymers as a template for metal-block copolymer nanocomposites formation. Organic-inorganic composites were prepared with Ag nanoparticles embedded within colloidal particles of an amphiphilic, thermally responsive polymer. To promote the incorporation of unaggregated Ag nanoparticles, temperature responsive microspheres of poly (N-isopropylacrylamide) (NIPAM) block with polystyrene were synthesized. Polyethyleneimine (PEI) could act as the linker between Ag ions (Ag nanoparticles) and poly (styrene-b-N-isopropylacrylamide) (PS-b-PNIPAM) colloids and the reducing agent in the formation of Ag nanoparticles. Transmission electron microscopy (TEM) measurements confirmed the nanostructures, ¹HNMR and FTIR characterized the components of the resulting nanoobjects. These stimuli-responsive hybrid microspheres will have potential applications in biomedical areas, such as tissue engineering and drug delivery.     

Metal Oxide Heterostructure Array via Spatially Controlled–Growth within Block Copolymer Templates

Nanofabrication is continuously searching for new methodologies to fabricate 3D nanostructures with 3D control over their chemical composition. A new approach for heterostructure nanorod array fabrication through spatially controlled–growth of multiple metal oxides within block copolymer (BCP) templates is presented. Selective growth of metal oxides within the cylindrical polymer domains of polystyrene‐block‐poly methyl methacrylate is performed using sequential infiltration synthesis (SIS). Tuning the diffusion of trimethyl aluminum and diethyl zinc organometallic precursors in the BCP film directs the growth of AlO_x and ZnO to different locations within the cylindrical BCP domains, in a single SIS process. BCP removal yields an AlO_x‐ZnO heterostructure nanorods array, as corroborated by 3D characterization with scanning transmission electron microscopy (STEM) tomography and a combination of STEM and energy‐dispersive X‐ray spectroscopy tomography. The strategy presented here will open up new routes for complex 3D nanostructure fabrication.     

Synthesis of crosslinked poly(styrene-<Emphasis Type="Italic">co</Emphasis>-divinylbenzene-<Emphasis Type="Italic">co</Emphasis>-sulfopropyl methacrylate) nanoparticles by emulsion polymerization: Tuning the particle size and surface charge density

We have synthesized highly charged, crosslinked poly (styrene-co-divinylbenzene-co-sulfopropyl methacrylate) copolymer colloidal particles using emulsion polymerization. The effects of concentration of the emulsifier and the initiator on the particle size and the charge density of the colloidal particles are studied. Colloidal particle size is highly dependent upon the concentration of the emulsifier and the initiator. The colloidal particle diameter decreases with increasing concentration of the emulsifier and increases with increasing concentration of the initiator in the polymerization mixture. Number of particles, surface charge density and charges per particle are also functions of both the emulsifier and the initiator concentration. The surface charge density and the number of charges per sphere increase with increasing particle diameter. These copolymer colloid particles self assemble readily and diffract visible light. Polymer hydrogel imbibed with these colloids shows the light diffraction.     

A Simple Top‐Down/Bottom‐Up Approach to Sectored,Ordered Arrays of Nanoscopic Elements Using Block Copolymers

A top‐down/bottom‐up approach is demonstrated by combining electron‐beam (e‐beam) lithography and a solvent annealing process. Micellar arrays of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a high degree of lateral order can be produced on a surface where sectoring is defined by e‐beam patterning. The e‐beam is used to crosslink the block copolymer (BCP) film immediately after spin‐coating when the BCP is disordered or in a highly ordered solvent‐annealed film. Any patterns can be written into the BCP by crosslinking. Upon exposure to a preferential solvent for the minor component block followed by drying, cylindrical nanopores are generated within the nonexposed areas by a surface reconstruction process, while, in the exposed areas, the films remain unchanged. Nickel nanodot arrays can be placed over selected areas on a surface by thermal evaporation and lift‐off process.     

Structure-property relationship of specialty elastomer-clay nanocomposites

The present work deals with the synthesis of specialty elastomer [fluoroelastomer and poly (styrene-b-ethylene-co-butylene-b-styrene (SEBS)]-clay nanocomposites and their structure-property relationship as elucidated from morphology studies by atomic force microscopy, transmission electron microscopy and X-ray diffraction and physico-mechanical properties. Due to polarity match, hydrophilic unmodified montmorillonite clay showed enhanced properties in resulting fluoroelastomer nanocomposites, while hydrophobic organo-clay showed best results in SEBS nanocomposites.     

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal‐free polyacrylonitrile‐containing block copolymers is described. A high‐molecular‐weight poly(acrylonitrile‐block‐methyl methacrylate) (PAN‐b‐PMMA) is synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self‐assembly behavior of PAN‐b‐PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as‐spin‐coated PAN‐b‐PMMA is microphase‐separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN‐b‐PMMA into mesoporous carbon thin films, the pore size and center‐to‐center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions.     

Improvement of ultrathin polystyrene film stability by addition of poly(styrene-stat-chloromethylstyrene) copolymer: An atomic force microscopy study

A method to improve the stability of ultrathin polystyrene (PS) films on SiO_x/Si substrate is introduced. In this method, interfacial interactions between PS film and substrate are enhanced by addition of poly(styrene-stat-chloromethylstyrene(ClMS)) copolymer containing 5 mol% of ClMS group. The resulting slight structural modification of the copolymer does not cause phase separation in the polymer blend. On the other hand, the existence of polar ClMS groups provides anchoring sites on the polar SiO_x surface via dipolar interactions. In this study, ratios of the copolymers are varied from 0 to 40 wt.% in the thin films resulting in a systematic increase of the interfacial interactions. The dewetting behaviors of all films subjected to the same annealing conditions are explored via atomic force microscopy. The analyses of root mean square roughness and dewetting area as a function of annealing time and copolymer ratio provide information about the film stability. Our results indicate that blending small quantity of the copolymer with PS significantly increases the stability of ultrathin films.     

Adhesion and growth of vascular smooth muscle cells in cultures on bioactive RGD peptide-carrying polylactides

The surface of poly(l-lactide) (PLLA) films deposited on glass coverslips was modified with poly(dl-lactide) (PDLLA), or 1:4 mixtures of PDLLA and PDLLA-b-PEO block copolymers, in which either none, 5% or 20% of the copolymer molecules carried a synthetic extracellular matrix-derived ligand for integrin adhesion receptors, the GRGDSG oligopeptide, attached to the end of the PEO chain. The materials, perspective for vascular tissue engineering, were seeded with rat aortic smooth muscle cells (11,000 cells/cm²) and the adhesion, spreading, DNA synthesis and proliferation of these cells was followed on inert and bioactive surfaces. In 24-h-old cultures in serum-supplemented media, the number of cells adhering to the PDLLA-b-PEO copolymer was almost eight times lower than that on the control PDLLA surface. On the surfaces containing 5% and 20% GRGDSG-PEO-b-PDLLA copolymer, the number of cells increased 6- and 3-fold respectively, compared to the PDLLA-b-PEO copolymer alone. On PDLLA-b-PEO copolymer alone, the cells were typically round and non-spread, whereas on GRGDSG-modified surfaces the cell spreading areas approached those found on PDLLA, reaching values of 991 μm² and 611 μm² for 5% and 20% GRGDSG respectively, compared to 958 μm² for PDLLA. The cells on GRGDSG-grafted copolymers were able to form vinculin-containing focal adhesion plaques, to synthesize DNA and even proliferate in a serum-free medium, which indicates specific binding to the GRGDSG sequences through their adhesion receptors.     

Size-tunable nanoparticles composed of dextran-b-poly(D,L-lactide) for drug delivery applications

Nanoparticles (NPs) formulated using self-assembly of block copolymers have attracted significant attention as nano-scaled drug delivery vehicles. Here we report the development of a biodegradable NP using self-assembly of a linear amphiphilic block copolymer, Dex-b-PLA, composed of poly(D,L-lactide), and dextran. The size of the NPs can be precisely tuned between 15 and 70 nm by altering the molecular weight (M _W) of the two polymer chains. Using doxorubicin as a model drug, we demonstrated that the NPs can carry up to 21% (w/w) of the drug payload. The release profile of doxorubicin from NPs showed sustained release for over 6 days. Using a rat model, we explored the pharmacokinetics profiles of Dex-b-PLA NPs, and showed proof-of-concept that long circulation lifetime of the NPs can be achieved by tuning the M _W of Dex-b-PLA block copolymer. While the terminal half-life of Dex-b-PLA NPs (29.8 h) was similar to that observed in poly(ethylene glycol)-coated (PEG-coated) NPs (27.0 h), 90% of the injected Dex-b-PLA NPs were retained in the blood circulation for 38.3 h after injection, almost eight times longer than the PEG-coated NPs. The area under curve (AUC) of Dex-b-PLA NPs was almost four times higher than PEG-based NPs. The biodistribution study showed lower accumulation of Dex-b-PLA NPs in the spleen with 19.5% initial dose per gram tissue (IDGT) after 24 h compared to PEG-coated poly(lactide-co-glycolide) (PLGA) NPs (29.8% IDGT). These studies show that Dex-b-PLA block copolymer is a promising new biomaterial for making controlled nanoparticles as drug delivery vehicles.      

A versatile approach for the fabrication of Au hollow nanoparticles based on poly(styrene-co-2-aminoethyl methacrylate) template

The hollow Au nanospheres were successfully prepared by the template method. The poly(styrene-co-2-aminoethyl methacrylate hydrochloride) (P(St-co-AEMH)) nanoparticles synthesized by the emulsion polymerization were used as the templates. After coating by Au colloidal nanoparticles and the formation of Au shells, the interior templates were etched out by sulfuric acid, leading to the formation of Au hollow nanospheres. The structure and morphology of the nanoparticles and hollow nanospheres were carefully investigated by the fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray analysis (EDX), wide-angle X-ray diffractometer (WAXD), and thermal gravimetric analysis (TGA) techniques.     

Fabrication of nanostructure and formation of nanocrystal for non-volatile memory

In this work, we have demonstrated that the nanocrystal created by combining the self-assembled block copolymer thin film with regular semiconductor processing can be applicable to non-volatile memory device with increased charge storage capacity over planar structures. Self-assembled block copolymer thin film for nanostructures with critical dimensions below photolithographic resolution limits has been used during all experiments. Nanoporous thin film from PS-b-PMMA diblock copolymer thin film with selective removal of PMMA domains was used to fabricate nanostructure and nanocrystal. We have also reported about surface morphologies and electrical properties of the nano-needle structure formed by RIE technique. The details of nanoscale pattern of the very uniform arrays using RIE are presented. We fabricated different surface structure of nanoscale using block copolymer. We also deposited Si-rich SiNx layer using ICP-CVD on the silicon surface of nanostructure. The deposited films were studied after annealing. PL studies demonstrated nanocrystal in Si-rich SiNx film on nanostructure of silicon.     

Preparation and characterization of optical-functional diblock copolymer brushes on hollow sphere surface via atom transfer radical polymerization

The optical-functional poly(methyl methacrylate)-block-Tb complex diblock copolymer brushes grafted from hollow sphere surface via atom transfer radical polymerization were investigated in this work. A sufficient amount of azo initiator was introduced onto hollow sphere surface firstly. Then the monomer methyl methacrylate was polymerized via surface-initiated reverse atom transfer radical polymerization using azo group modified hollow sphere as initiator. Following, the poly(methyl methacrylate) modified hollow sphere was used as maroinitiator for surface-initiated atom transfer radical polymerization of Tb complex. The samples were characterized by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, gel permeation chromatographer and transmission electron microscopy, respectively. The results indicated that the poly(methyl methacrylate) had grafted from hollow sphere surface and the average diameter of hollow core was about 1 μm. The optical properties of the poly(methyl methacrylate)-block-Tb copolymer modified hollow sphere were also reported.     

Hierarchical description of deformation in block copolymer TPEs

We report on the deformation behavior of commercially relevant lamellar and cylindrical tri-block copolymers poly (styrene-b-ethylene-co-butylene-b-styrene) (SEBS) with two different compositions. The structural changes that occur at various length scales have been studied using a simultaneous small- and wide-angle X-ray scattering (SAXS/WAXS) during uni-axial tensile deformation of the polygrain samples. SAXS provides information about changes that occur upon deforming the glassy cylindrical or lamellar PS domains. WAXS, on the other hand, is sensitive to the crystallographic structure of the rubbery mid-block. Deformation calorimetry has been used to determine the energetics involved. The combined results from the various techniques indicate that the deformation takes place in three stages. First, at small strains, dilation occurs in the rubbery phase. At intermediate strains, the hard lamellar or cylindrical domains undergo micro-buckling, which is associated with a downturn in the stress–strain curve. Finally, we interpret that at higher strains, the bent lamellar/cylindrical domains rotate in the stretching direction resulting in a significant shear on the rubbery mid-block. This in turn leads to strain-induced crystallization in these materials. Although we could not prove it by WAXS, deformation calorimetry (which is more sensitive than the WAXS) was utilized to show its presence.