A double hydrophilic block copolymer, poly(ethylene glycol)‐poly(3‐dimethyl (methacryloyloxyethyl) ammonium propane sulfonate) (PEG‐SB), is synthesized by reversible addition‐fragmentation transfer (RAFT) polymerization using PEG methyl ether (4‐cyano‐4‐pentanoate dodecyl trithiocarbonate) as a chain transfer agent. PEG‐SB forms multi‐layered microspheres with dipole‐dipole interactions of the SB side chains as the driving force. The PEG‐SB polymers show an upper critical solution temperature (UCST) and the UCST is controllable by the polymerization degree. The PEG‐SB microspheres are dissociated above the UCST and then monodispersed microspheres (∼1 μm) are obtained when the solution temperature is decreased below the UCST again. The disassociation/association of the microspheres is also controllable using the concentration of NaCl. These multi‐responsive microspheres could be a powerful tool in the field of nano‐biotechnology.
The present review focuses on the recent progress made in thin film orientation of semi‐conducting polymers with particular emphasis on methods using epitaxy and shear forces. The main results reported in this review deal with regioregular poly(3‐alkylthiophene)s and poly(dialkylfluorenes). Correlations existing between processing conditions, macromolecular parameters and the resulting structures formed in thin films are underlined. It is shown that epitaxial orientation of semi‐conducting polymers can generate a large palette of semi‐crystalline and nanostructured morphologies by a subtle choice of the orienting substrates and growth conditions.
Though great attention has been paid in constructing well‐defined nano‐structures via the self‐assembly of amphiphilic macromolecules, the self‐assembly of non‐amphiphilic macromolecules in nanodroplet has drawn less attention up to now. Recently, we prepared a temperature‐responsive PEG‐based branched polymer with disulfide bonds in its backbone via reversible addition–fragmentation chain transfer (RAFT) polymerization of 2‐(2‐methoxyethoxy) ethyl methacrylate, oligo(ethylene glycol) methacrylate, and N,N′‐cystamine bisacrylamide. Subsequently, we loaded the branched polymer into nanodroplets, and have found that the self‐assembly behaviors of this branched polymer in the nanodroplet are different from those in common solution. Bioreducible nanocapsules with tunable size can easily formed in nanodroplet even at high concentration.
A new method for fabricating hydrogels with intricate control over hierarchical 3D porosity using microfiber porogens is presented. Melt electrospinning writing of poly(ε‐caprolactone) is used to create the sacrificial template leading to hierarchical structuring consisting of pores inside the denser poly(2‐oxazoline) hydrogel mesh. This versatile approach provides new opportunities to create well‐defined multilevel control over interconnected pores with diameters in the lower micrometer range inside hydrogels with potential applications as cell scaffolds with tunable diffusion and transport of, e.g., nutrients, growth factors or therapeutics.
In this study, a new type of functional, self‐assembled nanostructure formed from porphyrins and polyamidoamine dendrimers based on hydrogen bonding in an aqueous solution is presented. As the aggregates formed are promising candidates for solar‐energy conversion, their photocatalytic activity is tested using the model reaction of methyl viologen reduction. The self‐assembled structures show significantly increased activity as compared to unassociated porphyrins. Details of interaction forces driving the supramolecular structure formation and regulating catalytic efficiency are fundamentally discussed.
The synthesis of a novel photoreactive poly(ethylene glycol) (PEG)‐based polymer with caged carbonyl groups is reported. We further demonstrate its use for the on‐demand fabrication of hydrogels. For rapid gelation, a hydrazide‐functionalized PEG is used as the second component for the hydrogel preparation. The photoreactive PEG‐based polymer is designed for controlled cleavage of the protecting groups upon exposure to UV light releases free aldehyde moieties, which readily react with hydrazide groups in situ. This hydrogel system may find applications in controlled release drug delivery applications, when combined with in situ gelation. Furthermore, the possibility of forming gels specifically upon UV irradiation gives an opportunity for 3D fabrication of degradable scaffolds.
Rocket‐like vesicles formed are composed of poly(acrylic aicd) (PMAA )/poly(ethylene glycol) (PEG) complex coated hollow silica spheres, and the structure and composition of the vesicles are characterized using TGA, 1H NMR, FTIR, and TEM. Although only one‐third of EG units of PEG brushes grafted to hollow silica spheres form the complex with PMAA via hydrogen bonding, the first “booster” layer composed of PMAA/PEG complex can provide secure encapsulation of model compound calcein blue under an acidic condition. The second “booster” layer composed of PEG brushes can be formed by changing acidic pH to 7.4 through the disassociation of the PMAA/PEG complex. A higher molecular weight PMAA exhibits a faster disassembly due to the formation of a looser PMAA/PEG complex on the surfaces of hollow silica spheres.
A novel and non‐cytotoxic self‐healing supramolecular elastomer (SE) is synthesized with small‐molecular biological acids by hydrogen‐bonding interactions. The synthesized SEs behave as rubber at room temperature without additional plasticizers or crosslinkers, which is attributed to the phase‐separated structure. The SE material exhibits outstanding self‐healing capability at room temperature and essential non‐cytotoxicity, which makes it a potential candidate for biomedical applications.
Composite nanoparticles from poly[(9,9‐di‐n‐octylfluoren‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,8‐diyl)] (F8BT) and poly(9,9‐di‐n‐hexylfluoren‐2,7‐diyl) (PF) with embedded inorganic nanoparticles (TiO2, CdSe, and CdSe/CdS) are prepared through kinetic trapping by rapid turbulent mixing in a multi‐inlet vortex mixer without the need for polymer functionalization. High contents of inorganic materials up to 50–60 wt% are realized for all composites. The influence of flow ratios, sodium dodecyl sulfate (SDS) concentration, and absolute flow rates on the particle size and morphology is studied. High water‐to‐THF ratios and high total flow rates around 2 m s−1 yield particle sizes below 50 nm. By adjusting these parameters, controlled particle sizes between 30 to several hundred nanometers are obtained. Composite particles from CdSe/CdS and F8BT or PF show a strong quenching of the polymer emission and near exclusive emission from the inorganic nanocrystal, which indicates an efficient energy transfer with fluorescence quantum yields of 23% for the F8BT/CdSe/CdS composites and 21% for the PF/CdSe/CdS composites. The dispersions are colloidally stable for several months.
Since the development of supramolecular chemical biology, self‐organised nano‐architectures have been widely explored in a variety of biomedical applications. Functionalized synthetic molecules with the ability of non‐covalent assembly in an aqueous environment are typically able to interact with biological systems and are therefore especially interesting for their use in theranostics. Nanostructures based on π‐conjugated oligomers are particularly promising as theranostic platforms as they bear outstanding photophysical properties as well as drug loading capabilities. This Feature Article provides an overview on the recent advances in the self‐assembly of intrinsically fluorescent nanoparticles from π‐conjugated small molecules such as fluorene or perylene based chromophores for biomedical applications.
A novel and robust route for the synthesis of a new amphiphilic brush copolymer, poly(glycidyl methacrylate)‐graft‐polyethylene glycol (PGMA‐g‐PEG), with high grafting densities of 97%–98% through a “grafting onto” method via carbon dioxide chemistry is reported. PGMA‐g‐PEG can self‐assemble and form stable spherical core–shell micelles in aqueous solution. Besides, the obtained PGMA‐g‐PEG polymer contains hydroxyurethane structures as the junction sites between the PGMA backbone and PEG side chain, which can be used for further modification.
The novel hyperbranched poly(methyl acrylate)‐block‐poly(acrylic acid)s (HBPMA‐b‐PAAs) are successfully synthesized via single‐electron transfer‐living radical polymerization (SET‐LRP), followed with hydrolysis reaction. The copolymer solution could spontaneously form unimolecular micelles composed of the hydrophobic core (PMA) and the hydrophilic shell (PAA) in water. Results show that the size of spherical particles increases from 8.18 to 19.18 nm with increased pH from 3.0 to 12.0. Most interestingly, the unique regular quadrangular prisms with the large microstructure (5.70 μm in length, and 0.47 μm in width) are observed by the self‐assembly of unimolecular micelles when pH value is below 2. Such self‐assembly behavior of HBPMA‐b‐PAA in solution is significantly influenced by the pH cycle times and concentration, which show that increased polymer concentration favors aggregate growth.
A supramolecular block copolymer is prepared by the molecular recognition of nucleobases between poly(2‐(2‐methoxyethoxy)ethyl methacrylate‐co‐oligo(ethylene glycol) methacrylate)‐SS‐poly(ε‐caprolactone)‐adenine (P(MEO2MA‐co‐OEGMA)‐SS‐PCL‐A) and uracil‐terminated poly(ethylene glycol) (PEG‐U). Because the block copolymer is linked by the combination of covalent (disulfide bond) and noncovalent (A U) bonds, it not only has similar properties to conventional covalently linked block copolymers but also possesses a dynamic and tunable nature. The copolymer can self‐assemble into micelles with a PCL core and P(MEO2MA‐co‐OEGMA)/PEG shell. The size and morphologies of the micelles/aggregates can be adjusted by altering the temperature, pH, salt concentration, or adding dithiothreitol (DTT) to the solution. The controlled release of Nile red is achieved at different environmental conditions.
Novel dual molecular‐ and ion‐recognition responsive poly(N‐isopropylacrylamide‐co‐benzo‐12‐crown‐4‐acrylamide) (PNB12C4) linear copolymers with benzo‐12‐crown‐4 (B12C4) as both guest and host units are prepared. The copolymers exhibit highly selective sensitivities toward γ‐cyclodextrin (γ‐CD) and Na+. The presence of γ‐CD induces the lower critical solution temperature (LCST) of PNB12C4 copolymer to shift to a higher value due to the formation of 1:1 γ‐CD/B12C4 host‐guest inclusion complexes, while Na+ causes a negative shift in LCST due to the formation of 2:1 “sandwich” B12C4/Na+ host‐guest complexes. Regardless of the complexation order, when γ‐CD and Na+ coexist with PNB12C4, competitive complexation actions of B12C4 as both guest and host units toward γ‐CD and Na+ finally form equilibrium 2:2:1 γ‐CD/B12C4/Na+ composite complexes, and the final LCST values of PNB12C4 copolymer reach almost the same level. The results provide valuable guidance for designing and applying PNB12C4‐based smart materials in various applications.
A series of high‐efficiency, full‐color fluorescent elastomers based on polysiloxane matrix prepared by an easy thiol‐ene “click” reaction is reported here. It is found for the first time that the same elastomer can emit transformable colors by conveniently altering the excitation wavelength because of the effect of energy transfer and the “fluorescence switch” of lanthanide ions. A fluent change in emission colors can also be feasible and conveniently reproducible by varying the stoichiometric ratio of lanthanide ions and rhodamine‐B in solution and in polymer elastomers. The obtained elastomers are further coated onto commercially available UV‐LED cells from the solution medium followed by an in situ cross‐linking step.
A novel and facile bottom‐up strategy for preparing core‐shell nanofibers with selectively localized carbon nanotubes is developed using hierarchical composite micelles of crystalline‐coil copolymer and carbon nanotubes as the building blocks. An amphiphilic di‐block copolymer of poly (p‐dioxanone) (PPDO) and PEG (polyethylene glycol) functionalized with pyrene moieties at the chain ends of PPDO blocks (Py‐PPDO‐b‐PEG) is designed for constructing composite micelles with multiwalled carbon nanotubes (MWCNTs). The self‐assembly of Py‐PPDO‐b‐PEG and MWCNTs is co‐induced by the crystallization of PPDO blocks and the π–π stacking interactions between pyrene moieties and MWCNTs, resulting in composite micelles with “shish kebab”‐like nanostructure. A mixture of composite micelles and polyvinyl alcohol (PVA) water solution is then used as the spinning solution for preparing electrospun nanofibers. The morphologies of the nanofibers with different composition are investigated by SEM and TEM. The results suggest that the MWCNTs selectively localized in the core of the nanofibers of MWCNTs/Py‐PPDO‐b‐PEG/PVA. The alignment and interfusion of composite micelles during the formation of nanofibers may confine the carbon nanotubes in the hydrophobic core region. In contrast, the copolymer without pyrene moieties cannot form composite micelles, thus these nanofibers show selective localization of MWCNTs in the PVA shell region.
This work describes the synthesis of π‐conjugated polymers possessing arylene and 1,3‐butadiene alternating units in the main chain by the reaction of α,β‐unsaturated ester/nitrile containing γ‐H with aromatic/heteroaromatic aldehyde compound. By using 4‐(4‐formylphenyl)‐2‐butylene acid ethyl ester as a model monomer, the different polymerization conditions, including catalyst, catalyst amount, and solvent, are optimized. The polymerization of 4‐(4‐formylphenyl)‐2‐butylene acid ethyl ester is carried out by refluxing in ethanol for 72 h with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as a catalyst to give a 1,3‐butadiene‐containing π‐conjugated polymer, poly(phenylene‐1,3‐butadiene), in 84.3% yield with and / (PDI) estimated as 6172 and 1.65, respectively. Based on this new methodology, a series of π‐conjugated polymers containing 1,3‐butadiene units with different substituents are obtained in high yields. A possible mechanism is proposed for the polymerization through a six‐membered ring transition state and then a 1,5‐H shift intermediate.
A simple and effective airflow method to prepare sandwich‐type block copolymer films is reported. The films are composed of three layers: vertically oriented nanocylinders align in both upper and bottom layers and irregular nanocylinders exist in the bulk of the film. The vertically oriented nanocylinders in both sides can provide high accessibility to ions and ensures the exchange of chemical species between the membrane and external environment, while the irregularly oriented nanocylinders in the middle part of the film can prolong the pathway of ions transportation and enhance ions selectivity.
Stimuli‐responsive poly(N‐isopropylacrylamide) nanogel with covalently labeled rhodamine B urea derivatives (P(NIPAM‐co‐RhBUA)) is utilized as a sensitive fluorescent probe for Cr3+ in aqueous solution, and its thermo‐induced tunable detection capacity is investigated. At 20 °C, non‐fluorescent nanogel can selectively bind with Cr3+ over some other metal ions, leading to prominent fluorescence OFF–ON switching due to the recognition of RhBUA with Cr3+. Upon heating above the phase transition temperature, enhanced fluorescence intensity is observed (≈61‐fold increase at 45 °C) for the nanogel in the presence of Cr3+, accompanied with an improved detection sensitivity, which suggest that hydrophobic microenvironment generated in the collapsed nanogel plays an active role for their detection performance.
Nine different perylene derivatives are prepared and their ability to initiate, when combined with an iodonium salt (and optionally N‐vinylcarbazole), a ring‐opening cationic photopolymerization of epoxides under very soft halogen lamp irradiation is investigated. One of them is particularly efficient under a red laser diode exposure at 635 nm and belongs now to the very few systems available at this wavelength. The photochemical mechanisms are studied by steady‐state photolysis, electron spin resonance spin trapping, fluorescence, cyclic voltammetry, and laser flash photolysis techniques.
