Self-assembly of Block Copolymers

Herein, poly[quaternized 2-(dimethylamino)ethyl methacrylate-b-lauryl methacrylate-b-(oligo ethylene glycol)methacrylate] (QPDMAEMA-b-PLMA-b-POEGMA) cationic amphiphilic triblock terpolymers were used as vehicles for the complexation/encapsulation of insulin (INS). The terpolymers self-assemble in spherical micelles with PLMA cores and mixed QPDMAEMA/POEGMA coronas in aqueous solutions. The cationic micelles were complexed via electrostatic interactions with INS, which contains anionic charges at pH 7. The solutions were colloidally stable in all INS ratios used. Light-scattering techniques were used for investigation of the complexation ability and the size and surface charge of the terpolymer/INS complexes. The results showed that the size of the complexes increases as INS ratio increases, while at the same time the surface charge remains positive, indicating the formation of clusters of micelles/INS complexes in the solution. Fluorescence spectroscopy measurements revealed that the conformation of the protein is not affected after the complexation with the terpolymer micellar aggregates. It was observed that as the solution ionic strength increases, the size of the QPDMAEMA-b-PLMA-b-POEGMA/INS complexes initially decreases and then remains practically constant at higher ionic strength, indicating further aggregation of the complexes. atomic force microscopy (AFM) measurements showed the existence of both clusters and isolated nanoparticulate terpolymer/protein complexes. Full article

In this paper, the formation of nanostructured triblock terpolymer polystyrene-b-poly(4-vinylpyridine)-b-poly(solketal methacrylate) (PS-b-P4VP-b-PSMA), polystyrene-b-poly(4-vinylpyridine)-b-poly(glyceryl methacrylate) (PS-b-P4VP-b-PGMA) membranes via block copolymer self-assembly followed by non-solvent-induced phase separation (SNIPS) is demonstrated. An increase in the hydrophilicity was observed after treatment of non-charged isoporous membranes from PS-b-P4VP-b-PSMA, through acidic hydrolysis of the hydrophobic poly(solketal methacrylate) PSMA block into a hydrophilic poly(glyceryl methacrylate) PGMA block, which contains two neighbored hydroxyl (–OH) groups per repeating unit. For the first time, PS-b-P4VP-b-PSMA triblock terpolymers with varying compositions were successfully synthesized by sequential living anionic polymerization. Composite membranes of PS-b-P4VP-b-PSMA and PS-b-P4VP-b-PGMA triblock terpolymers with ordered hexagonally packed cylindrical pores were developed. The morphology of the membranes was studied with scanning electron microscopy (SEM) and atomic force microscopy (AFM). PS-b-P4VP-b-PSMA triblock terpolymer membranes were further treated with acid (1 M HCl) to get polystyrene-b-poly(4-vinylpyridine)-b-poly(glyceryl methacrylate) (PS-b-P4VP-b-PGMA). Notably, the pristine porous membrane structure could be maintained even after acidic hydrolysis. It was found that membranes containing hydroxyl groups (PS-b-P4VP-b-PGMA) show a stable and higher water permeance than membranes without hydroxyl groups (PS-b-P4VP-b-PSMA), what is due to the increase in hydrophilicity. The membrane properties were analyzed further by contact angle, protein retention, and adsorption measurements. Full article

We investigated the micellar behavior of a series of asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers in different P4VP-selective alcoholic solvents. The micellar behavior was further correlated with the spectroscopic ellipsometry results obtained on swelling of PS and P4VP polymer films in the corresponding solvent vapors. The time-resolved (in situ) dynamic light scattering (DLS) measurements, in combination with (ex situ) electron microscopy imaging, revealed information about the aggregation state of PS-b-P4VP BCP in different alcohols and the effect of heat treatment. The ellipsometry measurements allowed us to estimate the difference in solvent selectivity toward PS/P4VP pair. Both DLS and ellipsometric studies suggested that less polar alcohols (i.e., 1-propanol, 1-butanol, and 1-pentanol) are likely to be close to each other in terms of their selectivity toward PS/P4VP pair, whereas more polar ethanol and methanol show the highest and the lowest affinity toward P4VP, respectively. Full article

Over the past decades, the development of nano-scale electronic devices and high-density memory storage media has raised the demand for low-cost fabrication methods of two-dimensional (2D) arrays of magnetic nanostructures. Here, we present a chemical solution deposition methodology to produce 2D arrays of cobalt ferrite (CFO) nanodots on Si substrates. Using thin films of four different self-assembled block copolymers as templates, ordered arrays of nanodots with four different characteristic dimensions were fabricated. The dot sizes and their long-range arrangement were studied with scanning electron microscopy (SEM) and grazing incident small-angle X-ray scattering (GISAXS). The structural evolution during UV/ozone treatment and the following thermal annealing was investigated through monitoring the atomic arrangement with X-ray absorption fine structure spectroscopy (EXAFS) and checking the morphology at each preparation step. The preparation method presented here obtains array types that exhibit thicknesses less than 10 nm and blocking temperatures above room temperature (e.g., 312 K for 20 nm diameter dots). Control over the average dot size allows observing an increase of the blocking temperature with increasing dot diameter. The nanodots present promising properties for room temperature data storage, especially if a better control over their size distribution will be achieved in the future. Full article

There is an urgent need for new strategies that allow the simultaneous detection and control of drug delivery. By making use of supramolecular host-guest interactions, a kind of pseudopolyrotaxanes, as a visualizable nanoscale drug carrier has been constructed by self-assembly of cucurbit[7]uril (CB[7]) with methoxy poly(ethylene glycol)-block-quaternized poly(4-vinyl pyridine) (mPEG-b-QP4VP) using 4-(chloromethyl)benzonitrile. Simple addition of CB[7] into an aqueous solution of mPEG-b-QP4VP resulted in noncovalent attachment of CB[7] to 4-cyanobenzyl-containing polymers, transforming the nonemissive mPEG-b-QP4VP micelles into highly fluorescent micelles. These pseudopolyrotaxanes micelles exhibited remarkable supramolecular assembly-induced emission enhancement and excellent biocompatibility, showing great potential for bioimaging applications. In addition, the efficient cellular uptake of the developed pseudopolyrotaxanes micelles loaded with the anticancer drug doxorubicin was a promising platform for simultaneous cell imaging and drug delivery, thereby widening their application in cancer theranostics. Full article

We report a new method of preparation of poly (butyl acrylate)-g-polystyrene/polystyrene blends by free-radical polymerization. Copolymerization of glycidyl (meth)acrylate with butyl acrylate is followed by a polymer analogous reaction of this copolymer with acrylic acid and subsequent copolymerization of the modified backbone with styrene. Investigation on the number of reactive groups per backbone chain and its molecular weight allows grafting efficiencies of about 35% to be reached, as well as low cross-linking. Blends of nanophase-separated copolymers having a backbone with M_n of around 50 kg/mol and 4 reactive groups per chain are transparent, with haze as low as 14%, tensile strength of around 22 MPa, and elongations at the break of around 3%. Correlation between morphology determined by transmission electron microscopy and properties of the blend is established. Full article

Solvent vapor annealing is as an effective and versatile alternative to thermal annealing to equilibrate and control the assembly of polymer chains in thin films. Here, we present scientific and practical aspects of the solvent vapor annealing method, including the discussion of such factors as non-equilibrium conformational states and chain dynamics in thin films in the presence of solvent. Homopolymer and block copolymer films have been used in model studies to evaluate the robustness and the reproducibility of the solvent vapor processing, as well as to assess polymer-solvent interactions under confinement. Advantages of utilizing a well-controlled solvent vapor environment, including practically interesting regimes of weakly saturated vapor leading to poorly swollen states, are discussed. Special focus is given to dual temperature control over the set-up instrumentation and to the potential of solvo-thermal annealing. The evaluated insights into annealing dynamics derived from the studies on block copolymer films can be applied to improve the processing of thin films of crystalline and conjugated polymers as well as polymer composite in confined geometries. Full article

Blue light-initiated alcoholic reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) using bis (acyl) phosphane oxide (BAPO) as the photo-initiator is developed to prepare diblock copolymer nano-objects. High monomer conversion (95%) was achieved within 2 h of blue light irradiation in an isopropanol/water mixture. Effects of solvent, light intensity, and reaction temperature on the polymerization kinetics were evaluated. Finally, the effect of reaction temperature on the morphologies of diblock copolymer nano-objects was investigated and two morphological phase diagrams were constructed at 25 and 70 °C. Transmission electron microscopy (TEM) measurement confirmed that increasing the reaction temperature promoted the evolution of higher order morphology. We believe this study will provide more mechanistic insights into alcoholic RAFT dispersion polymerization for the creation of diblock copolymer nano-objects with well-defined structures. Full article

High molecular weight waterborne ABA block copolymers of styrene (St) and 2-ethylhexyl acrylate (2EHA) containing hard and soft domains were synthesized by means of RAFT (mini)emulsion polymerization using a bifunctional symmetric S,S-dibenzyl trithiocarbonate (DBTTC) RAFT agent. Miniemulsion polymerization was initially used for the synthesis of the A-block, which forms hard domains, followed by 2EHA pre-emulsion feeding to build the B-block soft domains. Polymerization kinetics and the evolution of the Molecular Weight Distribution (MWD) were followed during the synthesis of different ABA block copolymers. The thermal properties of the final symmetric block copolymers were studied on dried films by means of DSC. It was found that the block copolymers have two glass transitions, which indicates the presence of a two-phase system. Phase separation was investigated by means of microscopic techniques (AFM and TEM) and SAXS, both of the particles in the latex form, as well as after film formation at room temperature and after different post-treatments. Films were annealed at temperatures well above the glass transition temperature (T_g) of the hard phase to study the bulk morphology of the films after complete particle coalescence. Moreover, for comparison purposes, the films were re-dissolved in THF, and films were again cast directly from the homogeneous THF solutions. As THF is a good solvent for both blocks, such films serve as a reference for the equilibrium morphology. Finally, DMTA studies of the films annealed at different temperatures were performed to correlate the morphology changes with the mechanical properties of the block copolymers. Full article

Double-shelled hollow (DSH) structures with varied inorganic compositions are confirmed to have improved performances in diverse applications, especially in lithium ion battery. However, it is still of great challenge to obtain these complex nanostructures with traditional hard templates and solution-based route. Here we report an innovative pathway for the preparation of the DSH nanospheres based on block copolymer self-assembly, metal–ligand coordination and atomic layer deposition. Polymeric composite micelles derived from amphiphilic block copolymers and ferric ions were prepared with heating-enabled micellization and metal–ligand coordination. The DSH nanospheres with Fe₂O₃ stands inner and TiO₂ outer the structures can be obtained with atomic layer deposition of a thin layer of TiO₂ followed with calcination in air. The coordination was carried out at room temperature and the deposition was performed at the low temperature of 80 °C, thus providing a feasible fabrication strategy for DSH structures without destruction of the templates. The cavity and the outer layer of the structures can also be simply tuned with the utilized block copolymers and the deposition cycles. These DSH inorganic nanospheres are expected to find vital applications in battery, catalysis, sensing and drug delivery, etc. Full article

Lamella-forming ABC triblock terpolymers are convenient building blocks for the synthesis of soft Janus nanoparticles (JNPs) by crosslinking the B domain that is “sandwiched” between A and C lamellae. Despite thorough synthetic variation of the B fraction to control the geometry of the sandwiched microphase, so far only Janus spheres, cylinders, and sheets have been obtained. In this combined theoretical and experimental work, we show that the blending of polybutadiene homopolymer (hPB) into lamella morphologies of polystyrene-block-polybutadiene-block-polymethylmethacrylate (SBM) triblock terpolymers allows the continuous tuning of the polybutadiene (PB) microphase. We systematically vary the volume fraction of hPB in the system, and we find in both experiments and simulations morphological transitions from PB-cylinders to perforated PB-lamellae and further to continuous PB-lamellae. Our simulations show that the hPB is distributed homogeneously in the PB microdomains. Through crosslinking of the PB domain and redispersion in a common solvent for all blocks, we separate the bulk morphologies into Janus cylinders, perforated Janus sheets, and Janus sheets. These studies suggest that more complex Janus nanostructures could be generated from ABC triblock terpolymers than previously expected. Full article

Using field-theoretic simulations based on a self-consistent field theory (SCFT) with or without finite compressibility, nanoscale mesophase formation in molten linear AB and ABC block copolymers is investigated in search of candidates for new and useful nanomaterials. At selected compositions and segregation strengths, the copolymers are shown to evolve into some new nanostructures with either unusual crystal symmetry or a peculiar morphology. There exists a holey layered morphology with Im3 symmetry, which lacks one mirror reflection compared with Im3m symmetry. Also, a peculiar cubic bicontinuous morphology, whose channels are connected with tetrapod units, is found to have Pn3m symmetry. It is shown that there is another network morphology with tripod connections, which reveals P432 symmetry. The optimized free energies of these new mesophases and their relative stability are discussed in comparison with those of double gyroids and double diamonds. Full article

In this work, we investigated the phase behavior of melts of block-copolymers with one charged block by means of dissipative particle dynamics with explicit electrostatic interactions. We assumed that all the Flory–Huggins χ parameters were equal to 0. We showed that the charge- correlation attraction solely can cause microphase separation with a long-range order; a phase diagram was constructed by varying the volume fraction of the uncharged block and the electrostatic interaction parameter λ (dimensionless Bjerrum length). The obtained phase diagram was compared to the phase diagram of “equivalent” neutral diblock-copolymers with the non-zero χ-parameter between the beads of different blocks. The neutral copolymers were constructed by grafting the counterions to the corresponding co-ions of the charged block with further switching off the electrostatic interactions. Surprisingly, the differences between these phase diagrams are rather subtle; the same phases in the same order are observed, and the positions of the order-disorder transition ODT points are similar if the λ-parameter is considered as an “effective” χ-parameter. Next, we studied the position of the ODT for lamellar structure depending on the chain length N. It turned out that while for the uncharged diblock copolymer the product χ_crN was almost independent of N, for the diblock copolymers with one charged block we observed a significant increase in λ_crN upon increasing N. This can be attributed to the fact that the counterion entropy prevents the formation of ordered structures, and its influence is more pronounced for longer chains since they undergo the transition to ordered structures at smaller values of λ, when the electrostatic energy becomes comparable to k_bT. This was supported by studying the ODT in diblock-copolymers with charged blocks and counterions cross-linked to the charged monomer units. The ODT for such systems was observed at significantly lower values of λ, with the difference being more pronounced at longer chain lengths N. The fact that the microphase separation is observed even at zero Flory–Huggins parameter can be used for the creation of “high-χ” copolymers: The incorporation of charged groups (for example, ionic liquids) can significantly increase the segregation strength. The diffusion of counterions in the obtained ordered structures was studied and compared to the case of a system with the same number of charged groups but a homogeneous structure; the diffusion coefficient along the lamellar plane was found to be higher than in any direction in the homogeneous structure. Full article

To achieve a high stability in physiological environment and rapid intracellular drug release, a biodegradable zwitterionic triblock copolymer with a disulfide-linked poly-ε-caprolactone and polycarboxybetaine methacrylate (PCBMA-SS-PCL-SS-PCBMA) was prepared for micellar carrier to delivery doxorubicin (DOX) into tumor cells. PCBMA-SS-PCL-SS-PCBMA was obtained by following steps: i) introducing disulfide bonds through end-group modification of PCL diol with cystamine dihydrochloride; ii) preparing PCL-RAFT macromolecular chain transfer agent by EDC/NHS chemistry; iii) RAFT polymerization of zwitterionic monomer. Self-assembling from PCBMA-SS-PCL-SS-PCBMA, polymeric micelles had many advantages, such as ultra-low protein absorption in serum and obvious reduction-responsiveness in the presence of DTT. Furthermore, DOX-loaded micelles exhibited high stability upon centrifugation and lyophilization, a fast intracellular drug release and enhanced drug efficacy due to GSH-triggered PCBMA shell shedding and micellar reassembling. Thus, the polymeric micelles integrated several functions and properties could be prospectively utilized as valuable nanocarriers in cancer chemotherapeutics. Full article

Herein, a new process to manufacture multicore micelles nanoparticles reinforced with co-assembly via hydrophobic interaction and electrostatic interaction under the help of ultrasonication was developed. The precise co-assembly between negative/hydrophobic drug and positive charged amphiphilic copolymer based pluronic platform allows the formation of complex micelles structures as the multicore motif with predefined functions. In this study, curcumin was selected as a drug model while positively charged copolymer was based on a pluronic-conjugated gelatin with different hydrophobicity length of Pluronic F87 and Pluronic F127. Under impact of dual hydrophobic and electrostatic interactions, the nCur-encapsulated core–shell micelles formed ranging from 40 nm to 70 nm and 40–100 nm by transmission electron microscopy (TEM) and Dynamic Light Scattering (DLS), respectively. It is found that the structures emerged depended on the relative lengths of the hydrophobic blocks in pluronic. Regarding g2(τ) behavior from DLS measurement, the nanogels showed a high stability in spherical form. Surprisingly, the release profiles showed a sustainable behavior of Cur from this system for drug delivery approaches. In vitro study exhibited that nCur-encapsulated complex micelles increased inhibitory activity against cancer cells growth with IC₅₀ is 4.02 ± 0.11 mg/L (10.92 ± 0.3 µM) which is higher than of free curcumin at 9.40 ± 0.17 mg/L (25.54 ± 0.18 µM). The results obtained can provide the new method to generate the hierarchical assembly of copolymers with incorporated loading with the same property. Full article

The CO₂ absorption of liquid crystalline phases of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic L92, (EO)₈(PO)₄₇(EO)₈), monoethanolamine (MEA), and water, with a composition of 60% L92/10% MEA/30% water has been investigated to assess potential use in carbon capture and storage applications. Vapor–liquid equilibrium data of the liquid crystalline system with CO₂ was recorded up to a CO₂ partial pressure of 6 bar, where a loading of 38.6 g CO₂/kg sample was obtained. Moreover, the phase transitions occurring during the loading process were investigated by small angle X-ray scattering (SAXS), presenting a transition from lamellar + hexagonal phase to hexagonal (at 25 °C). In addition, the rheology of samples with varying loadings was also studied, showing that the viscosity increases with increasing CO₂-loading until the phase transition to hexagonal phase is completed. Finally, thermal stability experiments were performed, and revealed that L92 does not contribute to MEA degradation. Full article