Self-assembly Of Diblock Copolymers Research Articles

Tuning of the Morphology and Optoelectronic Properties of ZnO/P3HT/P3HT- b-PEO Hybrid Films via Spray Deposition Method.

The self-assembly of amphiphilic diblock copolymers yields the possibility of using them as a template for tailoring the film morphologies of sol-gel chemistry-derived inorganic electron transport materials, such as mesoporous ZnO and TiO2. However, additional steps including etching and backfilling are required for the common bulk heterojunction fabrication process when using insulating diblock copolymers. Here, we use the conducting diblock copolymer poly(3-hexylthiophene)- block-poly(ethylene oxide) (P3HT- b-PEO) in which P3HT acts as charge carrier transport material and light absorber, whereas PEO serves as a template for ZnO synthesis. The initial solution is subsequently spray-coated to obtain the hybrid film. Scanning electron microscopy and grazing-incidence small-angle X-ray scattering measurements reveal a significant change in the morphology of the hybrid films during deposition. Optoelectronic properties illustrate the improved charge separation and charge transfer process. Both the amount of the diblock copolymer and the annealing temperature play an important role in tuning the morphology and the optoelectronic properties. Hybrid films being sprayed from a solution with the ratio of ωZnO, ωP3HT, and ωP3HT- b-PEO of 2:1:1 and subsequent annealing at 80 °C show the most promising morphology combined with an optimal photoluminescence quenching. Thus, the presented simple, reagent- and energy-saving fabrication method provides a promising approach for a large-scale preparation of bulk heterojunction P3HT/ZnO films on flexible substrates.

Topology optimization of multiple anisotropic materials, with application to self-assembling diblock copolymers

We propose a solution strategy for a multimaterial minimum compliance topology optimization problem, which consists in finding the optimal allocation of a finite number of candidate (possibly anisotropic) materials inside a reference domain, with the aim of maximizing the stiffness of the body. As a relevant and novel application we consider the optimization of self-assembled structures obtained by means of diblock copolymers. Such polymers are a class of self-assembling materials which spontaneously synthesize periodic microstructures at the nanoscale, whose anisotropic features can be exploited to build structures with optimal elastic response, resembling biological tissues exhibiting microstructures, such as bones and wood. For this purpose we present a new generalization of the classical Optimality Criteria algorithm to encompass a wider class of problems, where multiple candidate materials are considered, the orientation of the anisotropic materials is optimized, and the elastic properties of the materials are assumed to depend on a scalar parameter, which is optimized simultaneously to the material allocation and orientation. Well-posedness of the optimization problem and well-definition of the presented algorithm are narrowly treated and proved. The capabilities of the proposed method are assessed through several numerical tests.

Multifunctional Vesicles from a Self-assembled Cluster-Containing Diblock Copolymer.

We describe a new diblock copolymer composed of two segments with complementary functionalities. One block contains pendent photo-cross-linkable cinnamoyl groups, and the other contains molecular clusters, Co6Se8, capable of multielectron redox processes. This multifunctional macromolecule is synthesized by sequential ring-opening metathesis polymerization of monomers constructed using norbornene moieties. Remarkably, the tethered molecular cluster gives access to three different charge states in N, N-dimethylformamide: neutral, +1, and +2. In tetrahydrofuran, by contrast, the charged copolymer self-assembles into vesicles that inhibit the redox reactions. The wall of these vesicles can be cross-linked by exploiting the photoinduced 2 + 2 cycloaddition of the cinnamoyls to form cyclobutane dimers. Moreover, these vesicles can be loaded with molecular cargo and used as cross-linkable containers; we demonstrate this feature by encapsulating the molecular dye methylene blue into the capsules. Our work is the first report of a well-defined block copolymer containing a metal chalcogenide molecular cluster; more generally, it opens the door to new applications of metal-containing polymers.

Tailoring uniform gold nanoparticle arrays and nanoporous films for next-generation optoelectronic devices

High-density arrays of gold nanodots and nanoholes on indium tin oxide (ITO)-coated glass surfaces are fabricated using a nanoporous template fabricated by the self-assembly of diblock copolymers of poly (styrene-block-methyl methacrylate) (PS-b-PMMA) structures. By balancing the interfacial interactions between the polymer blocks and the substrate using random copolymer, cylindrical block copolymer microdomains oriented perpendicular to the plane of the substrate have been obtained. Nanoporous PS films are created by selectively etching PMMA cylinders, a straightforward route to form highly ordered nanoscale porous films. Deposition of gold on the template followed by lift off and sonication leaves a highly dense array of gold nanodots. These materials can serve as templates for the vapor-liquid-solid (VLS) growth of semiconductor nanorod arrays for next generation hybrid optoelectronic applications.

Dual Orthogonal Switching of the “Schizophrenic” Self-Assembly of Diblock Copolymers

Based on diblock copolymers, a pair of “schizophrenic” micellar systems is designed by combining a nonionic and thermoresponsive block with a zwitterionic block, which is thermoresponsive and salt-sensitive. The nonionic block is poly(N-isopropylacrylamide) (PNIPAM) or poly(N-isopropylmethacrylamide) (PNIPMAM) and exhibits a lower critical solution temperature (LCST) behavior in aqueous solution. The zwitterionic block is a polysulfobetaine, i.e., poly(4-((3-methacrylamidopropyl)dimethylammonio)butane-1-sulfonate) (PSBP), and has an upper critical solution temperature (UCST) behavior with the clearing point decreasing with increasing salt concentration. The PSBP-b-PNIPAM and PSBP-b-PNIPMAM diblock copolymers are prepared by successive reversible addition–fragmentation chain transfer (RAFT) polymerizations. The PSBP block is chosen such that the clearing point of the homopolymer is significantly higher in pure water than the cloud point of PNIPAM or PNIPMAM. Using turbidimetry, 1H NMR, and small-angle neut...

The directed self-assembly of amphiphilic diblock copolymers in selective solvents

ABSTRACTThe directed self-assembly of diblock copolymers in solvents is studied systematically using a simulated annealing method. Effects of the shape, scale, and adsorption capacity of the induced surface on the morphology of the aggregates are examined. A variety of morphologies are predicted. By increasing the scale of induced surface, the micellar shape transforms from cylinder to sheet with a tail and finally to thin sheet without tail. The shape of induced surface determines the sheet’s shape, such as rounded and square. Configurations of hydrophobic blocks and interfacial energies are investigated by calculating the mean square end-to-end distances and the contact numbers between hydrophobic monomer and other species, respectively.

Modification of Structural and Magnetic Properties of Masked Co–Pt Films Induced by High-Energy Ion Implantation

Magnetic and structural properties of Co80Pt20 films were modified by controlled ion implantation through a dot-patterned mask for possible application in the mass production of patterned recording media. The dot patterns were fabricated using self-assembly of di-block copolymers. The effects of 14N + and 40Ar+ ion implantation at energies as high as 40 and 100 keV, respectively, were studied. Although both ions cause changes in the structural and magnetic properties, 40 Ar+ ion implantation leads to more significant changes. The structural changes, predicted using simulations and experimentally observed using X-ray diffraction, indicate a mixing of Co into the layers below, leading to layers richer in Pt at the top. Magnetic force microscopy measurements show an increase in domain width and domain wall thickness as a function of ion fluences. The results are analyzed with measurements of magnetic anisotropy constant and micromagnetic simulations.

Synthesis and self-assembly of a novel amphiphilic diblock copolymer consisting of isotactic polystyrene and 1,4-trans-polybutadiene-graft-poly(ethylene oxide).

Herein, a novel amphiphilic diblock copolymer consisting of isotactic polystyrene (iPS) and 1,4-trans-polybutadiene-graft-poly(ethylene oxide) (1,4-trans-PBD-g-PEO), iPS-b-(1,4-trans-PBD-g-PEO), was synthesized by the combination of living coordination copolymerization and graft copolymerization. iPS-b-1,4-trans-PBD was firstly synthesized via sequential monomer addition in the presence of 1,4-dithiabutandiyl-2,2′-bis(6-cumenyl-4-methylphenoxy) titanium dichloride (complex 1) activated by triisobutyl aluminum modified methylaluminoxane (MMAO). Moreover, hydroboration of double bonds in the 1,4-trans-PBD blocks were performed with 9-borabicyclo[3.3.1]nonane (9-BBN) and subsequent oxidation by NaOH/H2O2 to form hydroxyls. Consequently, PEO was grafted into the hydroxylated 1,4-trans-PBD block in terms of ring-opening polymerization of ethylene oxide with potassium/naphthalide as initiatior. We also described solvent-evaporation-induced self-assembly of iPS-b-1,4-trans-PBD in n-dodecane and iPS-b-1,4-trans-PBD-g-PEO in aqueous solution, which were selective solvent for 1,4-trans-PBD and for 1,4-trans-PBD-g-PEO blocks, respectively. In these cases, tetrahydrofuran (THF) was used as good and volatile solvent. These resultant iPS-containing diblock copolymers could self-assemble into spherical nano-micelles with an iPS core as amorphous agglomeration or a very low degree of crystallinity resulting from slow crystallization rate and nanoconfinement. In addition, after isothermal crystallization of iPS in the micellar cores self-assembled in n-dodecane at 120 °C for 3 hours, the micellar morphology changed from sphere-like to platelet-like. It was believed that isothermal crystallization of iPS induced the deformation of the micelles.

Nanopatterns of Surface-Bound EphrinB1 Produce Multivalent Ligand-Receptor Interactions That Tune EphB2 Receptor Clustering.

Here we present a nanostructured surface able to produce multivalent interactions between surface-bound ephrinB1 ligands and membrane EphB2 receptors. We created ephrinB1 nanopatterns of regular size (<30 nm in diameter) by using self-assembled diblock copolymers. Next, we used a statistically enhanced version of the Number and Brightness technique, which can discriminate-with molecular sensitivity-the oligomeric states of diffusive species to quantitatively track the EphB2 receptor oligomerization process in real time. The results indicate that a stimulation using randomly distributed surface-bound ligands was not sufficient to fully induce receptor aggregation. Conversely, when nanopatterned onto our substrates, the ligands effectively induced a strong receptor oligomerization. This presentation of ligands improved the clustering efficiency of conventional ligand delivery systems, as it required a 9-fold lower ligand surface coverage and included faster receptor clustering kinetics compared to traditional cross-linked ligands. In conclusion, nanostructured diblock copolymers constitute a novel strategy to induce multivalent ligand-receptor interactions leading to a stronger, faster, and more efficient receptor activation, thus providing a useful strategy to precisely tune and potentiate receptor responses. The efficiency of these materials at inducing cell responses can benefit applications such as the design of new bioactive materials and drug-delivery systems.

Tailoring the structural and magnetic properties of masked CoPt thin films using ion implantation

The effects of ion implantations through a mask on the structural and magnetic properties of Co80Pt20 films were investigated. The mask was patterned using the self-assembly of diblock copolymers. For implantation, high (40 keV for 14N+ and 100 keV for 40Ar+) and low (7.5 keV for 14N+ and 4.5 keV for 40Ar+) energy 14N+ and 40Ar+ ions were used to modify the structural and magnetic properties of these films. X-ray diffraction and TRIM simulations were performed for understanding the structural changes due to ion implantations. These results revealed the intermixing of Co atoms in lower layers and lattice expansion in Co80Pt20 magnetic and Ru layers. A lateral straggling of Co caused an increase in the exchange coupling in the masked region. Depletion of Co atoms in Co80Pt20 layer caused a decrease in the anisotropy constant, which were further confirmed by the alternating gradient force magnetometer and magnetic force microscopy results. The magnetic force microscopy images showed an increase in domain width and domain wall width confirming the above-mentioned effects.

Hierarchical “As-Electrospun” Self-Assembled Fibrous Scaffolds Deconvolute Impacts of Chemically Defined Extracellular Matrix- and Cell Adhesion-Type Interactions on Stem Cell Haptokinesis

Controlled self-assembly of diblock copolymers offers the possibility of fabricating multilength scale, three-dimensional (3D) porous/fibrous structures (or scaffolds) with defined internal nano- or microstructure, with opportunities for application in a variety of fields, ranging from energy storage to bioengineering. Traditional methods by which such 3D constructs are produced are time-consuming and tedious, hindering their broader exploitation within larger-scale industrial processes. We report the development of a one-step process to fabricate "as-electrospun" self-assembled diblock copolymer micro- to nanometer-sized fibers incorporating core-shell or lamellar, closely packed spheres or bicontinuous gyroid nanosized structures. Isotropic and anisotropic (aligned) porous mats presenting spatially controlled chemistries, including bioactive (peptide-based) motifs, were successfully made from these hierarchical fibers. When functionalized with peptide sequences derived from a cell adhesion molecule (E-cadherin) and an extracellular matrix glycoprotein (laminin), these novel materials provided new insight into the impacts of such exquisitely tailored contact-guidance cues on the haptokinesis of human mesenchymal stem cells.

Higher-order assembly of crystalline cylindrical micelles into membrane-extendable colloidosomes

Crystallization-driven self-assembly of diblock copolymers into cylindrical micelles of controlled length has emerged as a promising approach to the fabrication of functional nanoscale objects with high shape anisotropy. Here we show the preparation of a series of crystallizable diblock copolymers with appropriate wettability and chemical reactivity, and demonstrate their self-assembly into size-specific cylindrical micelle building blocks for the hierarchical construction of mechanically robust colloidosomes with a range of membrane textures, surface chemistries and optical properties. The colloidosomes can be structurally elaborated post assembly by in situ epitaxial elongation of the membrane building blocks to produce microcapsules covered in a chemically distinct, dense network of hair-like outgrowths. Our approach provides a route to hierarchically ordered colloidosomes that retain the intrinsic growth activity of their constituent building blocks to permit biofunctionalization, and have potential applications in areas such as biomimetic encapsulation, drug delivery, catalysis and biosensing.

Reactive oxygen species-responsive polymeric nanoparticles for alleviating sepsis-induced acute liver injury in mice.

Sepsis-associated acute liver injury contributes to the pathogenesis of multiple organ dysfunction syndrome and is associated with increased mortality. Currently, no specific therapeutics for sepsis-associated liver injury are available. With excess levels of reactive oxygen species (ROS) being implicated as key players in sepsis-induced liver injury, we hypothesize that ROS-responsive nanoparticles (NPs) formed via the self-assembly of diblock copolymers of poly(ethylene glycol) (PEG) and poly(propylene sulfide) (PPS) may function as an effective drug delivery system for alleviating sepsis-induced liver injury by preferentially releasing drug molecules at the disease site. However, there are no reports available on the biocompatibility and effect of PEG-b-PPS-NPs invivo. Herein, this platform was tested for delivering the promising antioxidant therapeutic molecule melatonin (Mel), which currently has limited therapeutic efficacy because of its poor pharmacokinetic properties. The mPEG-b-PPS-NPs efficiently encapsulated Mel using the oil-in-water emulsion technique and provided sustained, on-demand release that was modulated invitro by the hydrogen peroxide concentration. Animal studies using a mouse model of sepsis-induced acute liver injury revealed that Mel-loaded mPEG-b-PPS-NPs are biocompatible and much more efficacious than an equivalent amount of free drug in attenuating oxidative stress, the inflammatory response, and subsequent liver injury. Accordingly, this work indicates that mPEG-b-PPS-NPs show potential as an ROS-mediated on-demand drug delivery system for improving Mel bioavailability and treating oxidative stress-associated diseases such as sepsis-induced acute liver injury.

Kinetics of Dynamic Polymer Brush Formation

The kinetics of dynamic polymer brush formation, which is driven by interfacial segregation of amphiphilic block copolymers, was investigated by quartz crystal microbalance (QCM) and neutron reflectivity (NR). High speed formation kinetics in the early stage was probed by QCM, and the later stage, where the formation kinetics became relatively slow, was investigated by NR. QCM detected fairly the fast brush formation kinetics on the order of tens of seconds for the copolymers in use. The dynamic polymer brush rapidly grows initially and hence repairs itself when the surface is damaged and the brush is partly lost. This fast dynamic polymer brush formation is driven by relatively slow diffusion of block copolymers in the matrix. The slow diffusion suggests that the diffusion mechanism is not controlled by simple Rouse or reputational diffusion but by the activation hopping mechanism of self-assembled diblock copolymers.

Polymerization-Induced Self-Assembly of Homopolymer and Diblock Copolymer: A Facile Approach for Preparing Polymer Nano-Objects with Higher-Order Morphologies.

Polymerization-induced self-assembly of homopolymer and diblock copolymer using a binary mixture of small chain transfer agent (CTA) and macromolecular chain transfer agent (macro-CTA) is reported. With this system, homopolymer and diblock copolymer were formed and chain extended at the same time to form polymer nano-objects. The molar ratio of homopolymer and diblock copolymer had a significant effect on the morphology of the polymer nano-objects. Porous vesicles, porous nanospheres, and micron-sized particles with highly porous inner structure were prepared by this method. We expect that this method will greatly expand the promise of polymerization-induced self-assembly for the synthesis of a range of polymer nano-objects with unique morphologies.

Hypoxia and H2O2 Dual-Sensitive Vesicles for Enhanced Glucose-Responsive Insulin Delivery.

A glucose-responsive closed-loop insulin delivery system mimicking pancreas activity without long-term side effect has the potential to improve diabetic patients' health and quality of life. Here, we developed a novel glucose-responsive insulin delivery device using a painless microneedle-array patch containing insulin-loaded vesicles. Formed by self-assembly of hypoxia and H2O2 dual-sensitive diblock copolymer, the glucose-responsive polymersome-based vesicles (d-GRPs) can disassociate and subsequently release insulin triggered by H2O2 and hypoxia generated during glucose oxidation catalyzed by glucose specific enzyme. Moreover, the d-GRPs were able to eliminate the excess H2O2, which may lead to free radical-induced damage to skin tissue during the long-term usage and reduce the activity of GOx. In vivo experiments indicated that this smart insulin patch could efficiently regulate the blood glucose in the chemically induced type 1 diabetic mice for 10 h.

Micellar nanocarriers for anticancer drug melanin

ABSTRACTThe effective biocompatible and partially biodegradable micellar nanocarriers for encapsulation of the anticancer drug eumelanin were created. Such nanocarries are the products of self-assembly of asymmetric diblock and triblock copolymers, which comprised chemically complementary (methoxy)poly(ethylene oxide) and poly(acrylic acid) blocks of a variable length. A chemical structure and solubility of the eumelanin, the vital activity product of black yeast “Nadsoniella nigra sp. X-1, was characterized. Peculiarities of the micellization process, morphology, size and stability of the developed micellar nanocarries were highlighted. The eumelanin encapsulation into micellar nanocarries with different morphology and a state of the obtained drug/micelle systems were studied and discussed.

Self-Assembly of AB Diblock Copolymer Confined in a Soft Nano-Droplet: A Combination Study by Monte Carlo Simulation and Experiment.

The self-assembly of AB-type diblock copolymers confined in a three-dimensional (3D) soft nanodroplet is investigated by the combination of Monte Carlo simulation and experiment. The influences of two critical factors, i.e., confinement degree of the imposed confinement space and the interfacial interaction between each individual block and boundary interface, on the 3D soft confined self-assembly are examined systematically. The simulation results reveal that block copolymer chains become more and more folded as the confinement degree (it can be monitored by the ratio of D/L, where L is the length of polymer chain and D is the reduced diameter of the final polymeric particle) is enhanced, causing a series of morphological transitions. Based on the simulation prediction, we perform the corresponding experiments by the 3D confined self-assembly of both symmetric and asymmetric block copolymers within the emulsion droplets. The experimental results well reproduce the confinement degree induced morphological transitions predicted by the simulations, such as the transition from segmented pupa-like particle to hamburger particle and the transition from raspberry-like particle to triangle-like particle, and then to hamburger particle. The current study implies that self-assembled nanostructures under 3D soft confinement can be simply controlled by tuning the confinement degree and interfacial property, i.e., the ratio of D/L and the interfacial interaction between each individual block and boundary interface.

High-Density Liquid-Crystalline Polymer Brushes Formed by Surface Segregation and Self-Assembly.

High-density polymer brushes on substrates exhibit unique properties and functions stemming from the extended conformations due to the surface constraint. To date, such chain organizations have been mostly attained by synthetic strategies of surface-initiated living polymerization. We show herein a new method to prepare a high-density polymer brush architecture using surface segregation and self-assembly of diblock copolymers containing a side-chain liquid-crystalline polymer (SCLCP). The surface segregation is attained from a film of an amorphous base polymer (polystyrene, PS) containing a minor amount of a SCLCP-PS diblock copolymer upon annealing above the glass-transition temperature. The polystyrene portion of the diblock copolymer can work as a laterally mobile anchor for the favorable self-assembly on the polystyrene base film.

Block copolymer morphologies confined by square-shaped particle: Hard and soft confinement**Project supported by the National Natural Science Foundation of China (Grant No. 20804060) and the Research Foundation of Chongqing University of Science and Technology, China (Grant No. CK2013B16).

The self-assembly of diblock copolymers confined around one square-shaped particle is studied systematically within two-dimensional self-consistent field theory (SCFT). In this model, we assume that the thin block copolymer film is confined in the vicinity of a square-shaped particle by a homopolymer melt, which is equivalent to the poor solvents. Multiple sequences of square-shaped particle-induced copolymer aggregates with different shapes and self-assembled internal morphologies are predicted as functions of the particle size, the structural portion of the copolymer, and the volume fraction of the copolymer. A rich variety of aggregates are found with complex internal self-assembled morphologies including complex structures of the vesicle, with one or several inverted micelle surrounded by the outer monolayer with the particle confined in the core. These results demonstrate that the assemblies of diblock copolymers formed around the square-shaped particle in poor solvents are of immediate interest to the assembly of copolymer and the morphology of biomembrane in the confined environment, as well as to the transitions of vesicles to micelles.