Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Free volume characteristics of 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene copolymers: Effect of composition and molecular weight

2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene (PDD-TFE) copolymer is a good candidate to prepare gas separation membranes with excellent permeability due to its free volume characteristics. However, the influence of PDD-TFE copolymer structure on its free volume characteristics is less studied. In this paper, PDD-TFE copolymers with different compositions and molecular weights were synthesized, and their free volume characteristics were analyzed by positron annihilation lifetime spectroscopy and a molecular dynamics simulation. It indicated that the molar fraction of PDD in copolymers had a significant effect on free volume characteristics, while the molecular weight of copolymers exerted a slight influence on free volume when the molecular weight exceeded a critical region (intrinsic viscosity [η] > 68 ml g⁻¹). PDD-TFE copolymers with greater PDD molar fractions (i.e., 72% and 84%) showed bimodal distributions in positron lifetime and free volume size distributions, while PDD-TFE copolymers with lower PDD molar fractions (i.e., 27% and 35%) exhibited a single peak. The long-lifetime parameter τ₃ was assigned to micro-cavities formed by [-(TFE)_y-PDD-] segments and τ₄ was attributed to micro-cavities formed by [-(PDD)_x-TFE-] segments. The cis and trans transitions of PDD led to a local multilayer spiral structure with a 2.6–4.3 Å layer spacing, which would also increase the free volume of copolymers.     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

Synthesis,self-assembly and photo-responsive behavior of AB2 shaped amphiphilic azo block copolymer

In this work, we report the synthesis of AB2 shaped amphiphilic azo block copolymer by macromolecular azo coupling reaction. The product and intermediates were characterized by various methods. The selfassembly in selected solvents and photo-responsive behavior of the copolymer were studied by means of UV–vis spectrophotometry and TEM. Spherical aggregates can be obtained by gradually adding water into the solution of this amphiphilic azo block copolymer. Upon irradiation with polarized UV(365 nm)light, the aggregates can be elongated in the polarized direction.     

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

Behavior of poly(ε-caprolactone)-based diblock copolymers in a bulk state and in solution

Abstract

A series of amphiphilic MOPEO-b-PCL copolymers (DBCs), based on biocompatible methoxypoly(ethylene oxide) with M_n=4.5?kDa and poly(ε-caprolactone) of a variable chain length, was synthesized by an anionic ring-opening block copolymerization. The structural investigations, performed by DSC and WAXS methods, revealed the microphase separation in DBC bulk structure and the existence of separate amorphous regions and microcrystalline domains of MOPEO and PCL blocks. Spectrophotometry and SLS were used to study the self-assembling of DBC macromolecules in selective dioxane/aqueous solution and to determine the main micellization parameters (CMC and -ΔG°). The DBC micelles morphology and their specific aggregation in mixed solvent were shown.     

Thermal properties and structure of electrospun blends of PVDF with a fluorinated copolymer

We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322     

A Micellar Mitotane Formulation with High Drug‐Loading and Solubility: Physico‐Chemical Characterization and Cytotoxicity Studies in 2D and 3D In Vitro Tumor Models

Adrenocortical carcinoma (ACC) is a rare tumor and prognosis is overall poor but heterogeneous. Mitotane (MT) has been used for treatment of ACC for decades, either alone or in combination with cytotoxic chemotherapy. Even at doses up to 6 g per day, more than half of the patients do not achieve targeted plasma concentration (14–20 mg L^?1) even after many months of treatment due to low water solubility, bioavailability, and unfavorable pharmacokinetic profile. Here a novel MT nanoformulation with very high MT concentrations in physiological aqueous media is reported. The MT‐loaded nanoformulations are characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, and powder X‐ray diffraction which confirms the amorphous nature of the drug. The polymer itself does not show any cytotoxicity in adrenal and liver cell lines. By using the ACC model cell line NCI‐H295 both in monolayers and tumor cell spheroids, micellar MT is demonstrated to exhibit comparable efficacy to its ethanol solution. It is postulated that this formulation will be suitable for i.v. application and rapid attainment of therapeutic plasma concentrations. In conclusion, the micellar formulation is considered a promising tool to alleviate major drawbacks of current MT treatment while retaining bioactivity toward ACC in vitro.     

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.     

Direct synthesis of Poly(Ԑ-Caprolactone)-block-poly (glycidyl methacrylate) copolymer and its usage as a potential nano micelles carrier for hydrophobic drugs

Ring-opening (ROP) and enzymatic copolymerization (ECP) are among the most widely used approaches for synthesizing copolymers of polycaprolactone (PCL). It involves multiple-step reactions and the utilization of enzymes that make the process a lot more complicated, time consuming, and expensive. Atom transfer radical polymerization (ATRP) has been adopted to synthesize a novel amphiphilic copolymer in our study. The study presents a method to eliminate the ROP/ECP multiple steps in monomer polymerization thus making the process simpler and smoother. The synthesis of cationic polymer micelles copolymer of PCL-PGMA (polycaprolactone grafted poly glycidyl methacrylate) was carried out using direct functionalization of hydroxy group in crude PCL to achieve a higher degree of functionalization, i.e., 12.8% for macroinitiator. FTIR and ¹H-NMR confirmed the successful synthesis of the copolymer with better control over the molecular weight with a PDI (1.84). DSC and XRD results showed the reduction of crystallinity by 86.81%, making copolymer more compatible for drug delivery application. The synthesized copolymer was further converted to nano-micelles drug carrier having an average size of 96.08 ± 21.22 nm. The drug encapsulation efficiency achieved was 60.0 ± 1.7%, and nano-micelles rendered a slow and controlled release of naproxen with long-term storage stability.