Induced Circular Dichroism to Optically Active Poly{[methyl(1‐naphthyl)silylene](o‐phenylene)methylene}s Assisted by Supramolecular Complexation with β‐Cyclodextrin

Summary: Optically active poly{methyl(1‐naphthyl)silylene](o‐phenylene)methylene}s with different molecular weights and configurations were prepared, and their supramolecular complexes with β‐cyclodextrin were investigated in a water–tetrahydrofuran mixture (1:1 v/v) at the temperatures between 25 and 68 °C. Complexation was very sensitive to sample preparation, molecular weight of the polymer as well as the configuration of the chiral silicon center. Supramolecular complexation, followed by changes in the circular dichroism, took place enantioselectively and the complex of the high‐molecular weight (+)‐polycarbosilane with β‐cyclodextrin exhibited a dramatic change in its induced circular dichroism. The mechanism of this unique complexation was investigated by SEC, ¹H NMR spectroscopy, UV, fluorescence, and circular dichroism.

Supramolecular complexation of β‐cyclodextrin with the optically active and isotactic polymer.     

Synthesis and Micellization of Star‐Shaped Poly(ethylene glycol)‐block‐Poly(ε‐caprolactone)

Summary: The relationship between the architecture of block copolymers and their micellar properties was investigated. Diblock, 3‐arm star‐shaped and 4‐arm star‐shaped block copolymers based on poly(ethylene glycol) and poly(ε‐caprolactone) were synthesized. Micelles of star‐shaped block copolymer in an aqueous solution were then prepared by a solvent evaporation method. The critical micelle concentration and the size of the micelles were measured by the steady‐state pyrene fluorescence method and dynamic light scattering, respectively. The CMC decreased in the order di‐, 3‐arm star‐shaped and 4‐arm star‐shaped block copolymer. The size of the micelles increased in the same order as the CMC. Theory also predicts that the formation of micelles becomes easier for 4‐arm star‐shaped block copolymers than for di‐ and 3‐arm star‐shaped block copolymers, which qualitatively agrees with the experiments.

     

Biocompatible Poly(D,L‐lactide)‐block‐Poly(2‐methacryloyloxyethylphosphorylcholine) Micelles for Drug Delivery

Well‐defined amphiphilic PLA‐b‐PMPC diblock copolymers were synthesized. Bimimetic micelles were prepared and applied for release of anti‐cancer drugs (DOX). TEM and DLS analysis revealed a regular spherical shape with small diameter (less than 50 nm) of the micelle. The biocompatibility of PLA‐b‐PMPC micelles was studied, and it was found that the micelles possessed excellent cytocompatibility due to the zwitterionic phosphorylcholine group. DOX could be efficiently loaded into the micelles with a loading efficiency of 44–67%. The DOX‐loaded micelles showed lower cytotoxicity than free drugs and efficiently delivered and released the drug into cancer cells. With these properties, the PLA‐b‐PMPC polymer micelles are attractive as drug carriers for pharmaceutical application.

     

Poly(ethylene imine)‐Triggered Morphological Change of Anisotropic Micelles from Direct Aqueous Self‐Assembly of an Amphiphilic Diblock Copolymer

In this paper, “star anise”‐like anisotropic micelle (AM) from direct aqueous self‐assembly of poly(ethylene oxide)‐block‐poly(p‐dioxanone) amphiphilic diblock copolymer is presented. By adding poly(ethylene imine) (PEI), the AM shows morphological change from “star anise” to swollen sphere. The mechanism of PEI‐triggered morphological transition involving complexation and weakening of crystallizability is revealed.

     

Ultrasound‐Induced Disruption of Amphiphilic Block Copolymer Micelles

Ultrasound‐induced disruption of PEO‐b‐PTHPMA, PEO‐b‐PIBMA, PEO‐b‐PTHFEMA, and PEO‐b‐PMMA block copolymer micelles in aqueous solution was investigated. Fluorescence change of loaded NR, DLS, IR, AFM, and SEM show that those micelles could be disrupted differently by 1.1 MHz high‐intensity focused ultrasound beams. The micelles of PEO‐b‐PIBMA and PEO‐b‐PTHPMA appear to be more sensitive to ultrasound irradiation, resulting in a more severe micellar disruption, and IR spectra show evidence of ultrasound‐induced chemical reactions, most likely hydrolysis. PEO‐b‐PMMA appear to resist HIFU irradiation better, and IR analysis found no evidence of chemical reactions. This study provides new evidence for the prospect of ultrasound‐responsive BCP micelles for controlled delivery applications.

     

pH‐Sensitive Micelles Formed by Interchain Hydrogen Bonding of Poly(methacrylic acid)‐block‐Poly(ethylene oxide) Copolymers

pH‐sensitive micelles formed by interchain hydrogen bonding of poly(methacrylic acid)‐block‐poly(ethylene oxide) copolymers were prepared and investigated at pH < 5. Both and R_h of the micelles increase with decreasing pH of the solution, displaying an asymptotic tendency at low pH values. The observed micelles are well‐defined nanoparticles with narrow size distributions (polydispersity ΔR_h/R_h ≤ 0.05) comparable with regular diblock copolymer micelles. The CMCs occur slightly below c = 1 × 10^?4 g · mL^?1. The micelles are negatively charged and their time stability is lower than that of regular copolymer micelles based purely on hydrophobic interactions.

     

Block Copolymer Micelles with an Intermediate Star‐/Flower‐Like Structure Studied by 1H NMR Relaxometry

¹H NMR relaxation is used to study the self‐assembly of a double thermoresponsive diblock copolymer in dilute aqueous solution. Above the first transition temperature, at which aggregation into micellar structures is observed, the trimethylsilyl (TMS)‐labeled end group attached to the shell‐forming block shows a biphasic T₂ relaxation. The slow contribution reflects the TMS groups located at the periphery of the hydrophilic shell, in agreement with a star‐like micelle. The fast T₂ contribution corresponds to the TMS groups, which fold back toward the hydrophobic core, reflecting a flower‐like micelle. These results confirm the formation of block copolymer micelles of an intermediate nature (i.e., of partial flower‐like and star‐like character), in which a part of the TMS end groups folds back to the core due to hydrophobic interactions.

     

Poly(hydroxyl propyl methacrylate)‐b‐Poly(oligo ethylene glycol methacrylate) Thermoresponsive Block Copolymers by RAFT Polymerization

Thermoresponsive amphiphilic poly(hydroxyl propyl methacrylate)‐b‐poly(oligo ethylene glycol methacrylate) block copolymers (PHPMA‐b‐POEGMA) are synthesized by RAFT polymerization, with different compositions and molecular weights. The copolymers are molecularly characterized by size‐exclusion chromophotography, and ¹H NMR spectroscopy. Dynamic light scattering (DLS) and static light scattering (SLS) experiments in aqueous solutions show that the copolymers respond to temperature variations via formation of self‐organized nanoscale aggregates. Aggregate structural characteristics depend on copolymer composition, molecular weight, and ionic strength of the solution. Fluorescence spectroscopy experiments confirm the presence of less hydrophilic domains within the aggregates at higher temperatures. The thermoresponsive behavior of the PHPMA‐b‐POEGMA block copolymers is attributed to the particular solubility characteristics of the hydrophilic, water insoluble PHPMA block that are modulated by the presence of the water soluble POEGMA block.     

Inorganic‐Salt‐Induced Morphological Transformation of Semicrystalline Micelles of PCL‐b‐PEO Block Copolymer in Aqueous Solution

The effect of inorganic salt at concentrations typical of a biological environment on the micellar morphology of semicrystalline PCL‐b‐PEO in aqueous solution is investigated. The salt is introduced either by dialysis of a THF solution against an aqueous solution of the salt or by adding it into an aqueous solution containing preformed micelles. The inorganic salt can induce sphere‐to‐rod or sphere‐to‐lamella transformations of the PCL‐b‐PEO micelles in aqueous solution, depending on the length of the PCL block. The inorganic salt induces “salting‐out” of the PEO block, leading to a decrease in the reduced tethering density of the corona in the micelles.

     

CO2‐Based Non‐ionic Surfactants: Solvent‐Free Synthesis of Poly(ethylene glycol)‐block‐Poly(propylene carbonate) Block Copolymers

Copolymerization of carbon dioxide (CO₂) and propylene oxide (PO) is employed to generate amphiphilic polycarbonate block copolymers with a hydrophilic poly(ethylene glycol) (PEG) block and a nonpolar poly(propylene carbonate) (PPC) block. A series of poly(propylene carbonate) (PPC) di‐ and triblock copolymers, PPC‐b‐PEG and PPC‐b‐PEG‐b‐PPC, respectively, with narrow molecular weight distributions (PDIs in the range of 1.05–1.12) and tailored molecular weights (1500–4500 g mol^?1) is synthesized via an alternating CO₂/propylene oxide copolymerization, using PEG or mPEG as an initiator. Critical micelle concentrations (CMCs) are determined, ranging from 3 to 30 mg L^?1. Non‐ionic poly(propylene carbonate)‐based surfactants represent an alternative to established surfactants based on polyether structures.

     

Effects of pH‐Sensitive Groups on Poly(ethylene oxide)‐block‐poly(ϵ‐caprolactone) Block Copolymer Micelles Used as Drug Carriers

A new type of drug delivery system consisting of an amphiphilic polymer micelle with pH‐sensitive groups is reported. The polymer comprises mPEG [poly(ethylene glycol) monomethyl ether], PCL [poly(?‐caprolactone)], and either PAA [poly(acrylic acid)] or PMAA [poly(methacrylic acid)]. Both mPEG‐b‐PCL and mPEG‐b‐PCL‐b‐PAA/PMAA are characterized by ¹H NMR, FTIR, and gel permeation chromatography (GPC). The diameters of the mPEG‐b‐PCL‐b‐PAA/PMAA micelles are found to increase with increases in pH and studies show that in vitro release of nifedipine from mPEG‐b‐PCL‐b‐PAA/PMAA micelles becomes faster as the pH value of phosphate‐buffered saline (PBS) increases. This new type of pH‐sensitive polymeric micelle can potentially be used as a drug carrier for oral administration of water‐insoluble drugs.     

Molecular Motions in the Supramolecular Complexes between Poly(ε‐caprolactone)‐Poly(ethylene oxide)‐Poly(ε‐caprolactone) and α‐ and γ‐Cyclodextrins

The structure and molecular motions of the triblock copolymer PCL‐PEO‐PCL and its inclusion complexes with α‐ and γ‐cyclodextrins (α‐ and γ‐CDs) have been studied by solid‐state NMR. Different cross‐polarization dynamics have been observed for the guest polymer and host CDs. Guest–host magnetization exchange has been observed by proton spin lattice relaxation T₁, proton spin lattice frame relaxation T_1ρ and 2D heteronuclear correlation experiments. A homogeneous phase has been observed for these complexes. Conventional relaxation experiments and 2D wide‐line separation NMR with windowless isotropic mixing have been used to measure the chain dynamics. The results show that for localized molecular motion in the megahertz regime, the included PCL block chains are much more mobile than the crystalline PCL blocks in the bulk triblock copolymer. However, the mobility of the included PEO block chains is not very different from the amorphous PEO blocks of the bulk sample. The cooperative, long chain motions in the mid‐kilohertz regime for pairs of PCL‐PEO‐PCL chains in their γ‐CD channels seem more restricted than for the single PCL‐PEO‐PCL chains in the α‐CD channels, however, they are not influencing the more localized, higher frequency megahertz motions.     

Mesh‐Like Vesicles Formed From Blends of Poly(4‐vinyl pyridine)‐b‐polystyrene‐b‐poly(4‐vinyl pyridine) Block Copolymers via Gradual Blending Method

In this study, we developed a novel blending strategy, namely, the gradual blending method, to tune the micellar structure. Different from the most commonly used premixing blending method, which different block copolymers are premixed in a common solvent before their individual self‐assembly, the gradual blending method involves gradually adding one type of block copolymer into the pre‐generated micellar solution formed from another type of block copolymer. Moreover, we obtained a novel mesh‐like vesicle from the self‐assembly of the mixtures of P4VP₄₃‐b‐PS₂₆₀‐b‐P4VP₄₃ and P4VP₄₃‐b‐PS₃₆₆‐b‐P4VP₄₃ in 1,4‐dioxane/water solution using the gradual blending method.     

Synthesis of Three Types of Amphiphilic Poly(ethylene glycol)‐block‐Poly(sebacic anhydride) Copolymers and Studies of their Micellar Solutions

Summary: Linear, three‐ and four‐armed block copolymers based on PEG and PSA were synthesized by melt polycondensation reactions. The CMC of the copolymer was measured using the dye solubilization method. The copolymers were found to self‐aggregate in water to form micelles above the CMC. The micellar solutions were prepared with different methods and investigated by DLS and AFM. The DLS method was used to measure the mean hydrodynamic diameters of the micelles. It was found that preparation method and condition of the micellar solution, as well as the structure and composition of the copolymer had effects on the hydrodynamic diameter of the copolymer micelles. AFM studies showed that the morphology of the micelle was spherical.

Synthesis of 3‐armed stars based on poly(ethylene glycol) and poly(sebacic anhydride).     

Synthesis of Poly[(ethylene terephthalate)‐co‐(ε‐caprolactone)]‐Poly(propylene oxide) Block Copolyester by Direct Polyesterification of Reactive Oligomers

Summary: The objective of this study was to synthesize thermoplastic elastomers by the direct copolyesterification of reactive oligomers of poly[(ethylene terephthalate)‐co‐(ε‐caprolactone)] (PET) and poly(propylene oxide) (PPO). The synthesis of hard segment oligomers was achieved in two steps. The first step consisted of the glycolysis of PET leading to α,ω‐hydroxyl functionalized oligomers. The second step corresponded to the ring opening polymerization of ε‐caprolactone onto the hydroxyl end groups of the PET oligomers. Commercially available hydroxytelechelic poly(propylene oxide) was modified to obtain carboxytelechelic poly(propylene oxide). The chemical structure of the product was investigated by ¹H NMR and size exclusion chromatography (SEC). Multiblock poly(ester‐ether) was then synthesized by polyesterification of hydroxytelechelic poly[(ethylene terephthalate)‐co‐(ε‐caprolactone)] with carboxytelechelic poly(propylene oxide) oligomers, using different catalysts and reaction conditions. The best stoichiometric ratio for the reaction was determined in order to obtain the highest possible . The chemical structure of the synthesized poly(ester‐ether) was investigated by size exclusion chromatography and ¹H NMR. The thermal and thermomechanical behavior of the synthesized poly(ester‐ether) was investigated by differential scanning calorimetry and dynamic mechanical analysis, which showed that the poly(ester‐ether) behaved as a thermoplastic elastomer. This product could also be an interesting way for chemical recycling of PET waste.

Synthesis of multiblock co‐poly(ester‐ether).     

Random Poly(methyl methacrylate‐co‐styrene) Brushes by ATRP to Create Neutral Surfaces for Block Copolymer Self‐Assembly

Random copolymer brushes of styrene and methyl methacrylate (MMA) on silicon wafers by atom transfer radical polymerization (ATRP) are synthesized using CuCl/CuCl₂/HMTETA. It is found that with increasing amount of styrene the thickness of the brush layer could no longer be well controlled by the amount of free (sacrificial) initiator in the reaction. At constant concentration of free initiator a constant thickness is obtained for various ratios of MMA to styrene. Within 30–70% MMA in the monomer feed the composition of the free polymer corresponds well to the monomer feed ratio, displaying a water contact angle in agreement with the theoretical value for a random copolymer. These copolymers are shown to create a neutral surface directing spin‐coated poly(styrene‐b‐MMA) into a perpendicular lamellae orientation.     

One‐Pot Synthesis of Micelles with a Cross‐Linked Poly(acrylic acid) Core

Summary: Stable micelles with polystyrene (PS) as a shell and cross‐linked poly[(acrylic acid)‐co‐(ethylene glycol diacrylate)] as a core have been successfully prepared by reversible addition fragmentation chain transfer (RAFT) copolymerization of acrylic acid and ethylene glycol diacrylate in a selective solvent with PS‐SC(S)Ph as a RAFT agent. For the preparation of stable micelles, the RAFT polymerizations are carried out in different solvents: benzene, cyclohexane, and mixtures of tetrahydrofuran and cyclohexane. The monomer/PS‐SC(S)Ph molar ratio and molecular weight of the macro‐RAFT agent, PS‐SC(S)Ph, influence the RAFT polymerization and the formation of micelles.

Block copolymerization in selective solvent with the RAFT agent.     

Micellization and the Surface Hydrophobicity of Amphiphilic Poly(vinylphenol)‐block‐Polystyrene Block Copolymers

The self‐assembly of PVPh‐b‐PS in different solvents was studied. Upon replacing toluene by THF as the solvent, the morphology of the resulting aggregates change from core‐shell spheres, rod‐like micelles and vesicles to onion‐like aggregates. With increasing block copolymer concentration, morphologies such as honeycomb‐like films, surfaces of aggregated large porous spheres, or pincushion‐like spheres with protruding tubular vesicle aggregates are observed. These surface‐patterned films show significantly enhanced hydrophobicity. The results suggest that a superhydrophobic behavior can be achieved, with a maximum contact angle of 158°, by using the pincushion‐like micellar structure.

     

Poly(ethylene oxide)‐ and Poly(perfluorohexylethyl methacrylate)‐Containing Amphiphilic Block Copolymers: Association Properties in Aqueous Solution

Amphiphilic di‐ and triblock copolymers containing poly(ethylene oxide) (PEO) as the hydrophilic block and poly(perfluorohexylethyl methacrylate) (PFMA) as the hydrophobic block were synthesized by atom‐transfer radical polymerization using hydroxy‐terminated PEO as the macroinitiator. The copolymers were characterized by size exclusion chromatography and ¹H NMR spectroscopy. Self‐association in aqueous solution has been investigated using surface tension measurements, dynamic light scattering (DLS), and transmission electron microscopy (TEM). From surface tension measurements in water, a characteristic concentration (c*) can be detected, which is interpreted as the critical micelle concentration (cmc). The cmc decreases with an increase in fluoro content in the triblock copolymer up to 11 wt.‐% PFMA (solubility limit). DLS studies have been carried out for different samples above the cmc, showing small aggregates (micelles) and single chains for diblock copolymer solutions. In the case of triblock copolymers large clusters were the dominant aggregates in addition to the micelles and single chains. The effect of temperature and concentration on the micelle and cluster formation has been investigated by DLS. Micelle size was found to be resistant to any change by temperature, however, a slight but significant increase in apparent hydrodynamic radius was observed with an increase in concentration, while both temperature and concentration affected the formation of large clusters, especially in concentrated solutions. TEM has been carried out to visualize the morphology of the aggregates after transferring the solution to carbon film. The initial concentration for the preparation of TEM samples was found to have a strong influence on the morphology of the aggregates. By adding colloidal gold particles to the solutions, the typical covering by the polymer was observed by TEM.

Decay‐rate distributions for PEO₁₀F5 (4.0 g · L^?1); obtained from the time correlation functions.     

Proton‐Conducting Poly(phenylene oxide)–Poly(vinyl benzyl phosphonic acid) Block Copolymers via Atom Transfer Radical Polymerization

Block copolymers containing poly(phenylene oxide) (PPO) and poly(vinyl benzyl phosphonic acid) segments are synthesized via atom transfer radical polymerization (ATRP). Monofunctional PPO blocks are converted into ATRP active macroinitiators, which are then used to polymerize a diethyl p‐vinylbenzyl phosphonate monomer in order to obtain phosphonated block copolymers bearing pendent phosphonic ester groups. Poly(phenylene oxide‐b‐vinyl benzyl phosphonic ester) block copolymers are hydrolyzed to corresponding acid derivatives to investigate their proton conductivity. The effect of the relative humidity (RH) is investigated. The proton conductivity at 50% RH and one bar of vapor pressure approaches 0.01 S cm^?1.