Star-Shaped Thermoplastic Elastomers Prepared via RAFT Polymerization.

Styrene-based thermoplastic elastomers (TPEs) demonstrate excellent overall performance and account for the largest industrial output. The traditional methods of preparation styrene-based thermoplastic elastomers mainly focused on anionic polymerization, and strict equipment conditions were required. In recent years, controlled/living radical polymerization (CRP) has developed rapidly, enabling the synthesis of polymers with various complex topologies while controlling their molecular weight. Herein, a series of core crosslinked star-shaped poly(styrene-b-isoprene-b-styrene)s (SISs) was synthesized for the first time via reversible addition-fragmentation chain transfer (RAFT) polymerization. Meanwhile, linear triblock SISs with a similar molecular weight were synthesized as a control. We achieved not only the controlled/living radical polymerization of isoprene but also investigated the factors influencing the star-forming process. By testing the mechanical and thermal properties and characterizing the microscopic fractional phase structure, we found that both the linear and star-shaped SISs possessed good tensile properties and a certain phase separation structure, demonstrating the characteristics of thermoplastic elastomers.

Preparation of Thermo- and pH-Responsive Microgels Based on Complementary Nucleobase Molecular Recognition.

Complementary interactions between the natural nucleobases is one of the important ways of biomolecular recognition. Although scientists have introduced such supramolecular noncovalent interactions into biomimetic materials through different approaches in recent years, further research is still needed to confer structural features of biomolecules into emerging stimuli-responsive microgels. In this study, a series of bis-thymine end decorated flexible poly (N-isopropyl acrylamide) (T-PNIPAM-T) are obtained through a thymine esterified RAFT agent. Meanwhile, a rigid polymeric backbone poly[1-(4-vinyl benzyl)] adenine (PS A), including several pendant adenines on the side chain is prepared. Through nucleobase complementary pairing subtle supramolecular cross-linked 3D networks are constructed, and further self-assembled to form microgels under the balance between hydrophilicity and block flexibility. More importantly, such supramolecular 3D microgels show volumetric shrinkage in different water content environments and the assembly behavior under thermo and pH stimulated conditions. This exploration is expected to play an important value and significance in the field of biomimetic controlled release of soft matter in the future.

Facile Synthesis of CO2 -Responsive Nano-Objects: Batch versus Semi-Batch RAFT Copolymerization.

Precise polymer architecture and self-assembled morphological control are attractive due to their promising applications, such as drug delivery, biosensors, tissue engineering and "smart" optical systems. Herein, starting from the same hydrophilic units poly(ethylene glycol) (PEG), using CO2 -sensitive monomer N, N-diethylaminoethyl methacrylate (DEAEMA) and hydrophobic monomer benzyl methacrylate (BzMA), a series of well-defined statistical, block, and gradient copolymers is designed and synthesized with similar degree of polymerization but different monomer sequences by batch and semi-batch RAFT polymerization process and their CO2 -responsive behaviors of these nano-objects is systematically studied. The gradient copolymers are generated by using semi-batch methods with programmed monomer feed rate controlled by syringe pumps, achieving precise control over desired gradient copolymer composition distribution. In aqueous solution, the copolymers could self-assemble into various aggregates before CO2 stimulus. Upon bubbling CO2 , the gradient copolymers preferred to form nanosheet-like structures, while the block and statistical copolymers with similar molar mass could only form larger vesicles with thinner membrane thickness or disassemble. The semi-batch strategy to precisely control over the desired composition distribution of the gradient segment presents an emerging trend for the fabrication and application of stimuli-responsive polymers.

Gas-Responsive Self-Assemblies for Mimicking the Alveoli.

In human body, alveoli are the primary sites for gas exchange which are formed by the dilation and protrusion of bronchioles at the end of the lung, and the rapid gas-exchanging process in the alveoli ensures normal life activities. Based on the unique structures and functions of alveoli, it is necessary to study the regulation mechanism of its formation, respiration, and apoptosis. Herein, a class of reversible addition-fragmentation chain transfer (RAFT)-derived amphiphilic triblock copolymers, PEO-b-P(DEAEMA-co-FMA)-b-PS is designed and synthesized. Due to the amphiphilic and gas-responsive segments, these triblock copolymers can self-assemble in aqueous solution and undergo the morphological transition from nanotubes to vesicles under gas stimulation; meanwhile, in the cycles of CO2 /O2 stimulation, these vesicles can further realize the volume expansion and contraction, eventually rupture. The gas-driven morphological transformations of these aggregates successfully imitate the formation, respiration, and apoptosis of alveoli, and provide an essential basis for revealing the life phenomena.

Modification of Electrospun Regenerate Cellulose Nanofiber Membrane via Atom Transfer Radical Polymerization (ATRP) Approach as Advanced Carrier for Laccase Immobilization.

This study aimed to modify an electrospun regenerated cellulose (RC) nanofiber membrane by surface grafting 2-(dimethylamino) ethyl methacrylate (DMAEMA) as a monomer via atom transfer radical polymerization (ATRP), as well as investigate the effects of ATRP conditions (i.e., initiation and polymerization) on enzyme immobilization. Various characterizations including XPS, FTIR spectra, and SEM images of nanofiber membranes before and after monomer grafting verified that poly (DMAEMA) chains/brushes were successfully grafted onto the RC nanofiber membrane. The effect of different ATRP conditions on laccase immobilization was investigated, and the results indicated that the optimal initiation and monomer grafting times were 1 and 2 h, respectively. The highest immobilization amount was obtained from the RC-Br-1h-poly (DMAEMA)-2h membrane (95.04 ± 4.35 mg), which increased by approximately 3.3 times compared to the initial RC membrane (28.57 ± 3.95 mg). All the results suggested that the optimization of initiation and polymerization conditions is a key factor that affects the enzyme immobilization amount, and the surface modification of the RC membrane by ATRP is a promising approach to develop an advanced enzyme carrier with a high enzyme loading capacity.

Templated Polymerization of Nucleobase Complexes via Molecular Recognition.

Macromolecules have a strong tendency to interact with each other in solution to form a supramolecular structure through various secondary binding forces. In this study, nucleobase-containing templates poly(9-(4-vinylbenzyl)adenine) (PS AH) and poly(1-(4-vinylbenzyl)cytosine) (PS CH) are prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. Vinylbenzyl thymine (MS T) is polymerized in the presence of these two nucleobase-containing templates. MS T shows higher affinities toward the template PS AH compared with the template PS CH. In accordance with the Watson-Crick pairing principle, thymine forms hydrogen bonding (H-bonding) with adenine, but not between thymine and cytosine. A complex is formed when PS AH is used as template which indicates that there is a template polymerization of nucleobase complexes via molecular recognition.

Cell-Penetrating, Peptide-Based RAFT Agent for Constructing Penetration Enhancers.

Peptide-polymer conjugates represent a promising class of compounds that can be used to overcome some of the limitations associated with peptides intended for therapeutic and diagnostic applications. The efficient generation of well-defined peptide/protein-polymer conjugates can promote the development of the design and synthesis of functional drugs and gene delivery platforms. In this research, a sequence defined cell penetrating peptide (i.e., Transportan 10 (TP 10))-based chain transfer agent (TP-CTA) was designed and synthesized in an automated peptide synthesizer. Thereafter, amphiphilic block copolymers poly[oligo(ethylene glycol) methyl ether acrylate]-b-poly(n-butyl acrylate) (TP-POEGA-b-PBA) were synthesized using the TP-CTA via reversible addition-fragmentation chain transfer (RAFT) polymerization. Circular dichroism (CD) spectroscopy confirmed the preservation of α-helix structure of TP 10, which is crucial for its bioactivity. Transmission electron microscopy (TEM) revealed the formation of self-assembled rod-like and vesicle nanostructures in an aqueous environment. Finally, the obtained peptide-conjugated block copolymers were demonstrated to be effective compounds for cell penetration. This method opens up a way for accessing peptide-polymer conjugates with cell-penetrating abilities.

Enzyme Degassing for Oxygen-Sensitive Reactions in Open Vessels of an Automated Parallel Synthesizer: RAFT Polymerizations.

An enzyme degassing method for oxygen-intolerant polymerizations was implemented in a commercially available automated parallel synthesizer and tested for reversible addition-fragmentation chain transfer (RAFT) polymerizations performed in open vessels. For this purpose, a recently reported methodology that employs the enzyme glucose oxidase (GOx) to deplete oxygen in reaction media was utilized. The effectiveness of this approach to perform unattended parallel polymerization reactions in open vessels was demonstrated by comparing experimental results to those obtained under similar experimental conditions but utilizing the common degassing method of sparging N2 to remove oxygen. The proposed experimental technique displayed good precision in performing RAFT polymerizations and good control of the obtained polymers and could be easily adapted to other systems where the removal of oxygen is mandatory. This alternative high-throughput/high-output method may have the potential to increase productivity in research projects where oxygen-intolerant reactions are involved.

Spindle-like and telophase-like self-assemblies mediated by complementary nucleobase molecular recognition.

Inspired by nature, supramolecular nanoparticles based on complementary nucleobase interactions have aroused wide interest. In our study, two kinds of fluorophores were conjugated at the end of nucleobase containing homopolymers, which can be used to confirm the binding state and calculate the binding constants among different nucleobase pairs. Furthermore, we describe a facile synthesis of nucleobase-functionalized amphiphilic polymers with rigid and flexible backbones using RAFT polymerization. Spindle-like or telophase-like supramolecular self-assemblies were formed by different components of such synthetic amphiphilic polymers.

How the Crosslinking Agent Influences the Thermal Stability of RTV Phenyl Silicone Rubber.

In this work, a thermal degradation mechanism of room temperature vulcanized (RTV) phenyl silicone rubber that was vulcanized by different crosslinking agents was discussed. Firstly, RTV phenyl silicone rubber samples were prepared by curing hydroxyl-terminated polymethyldiphenylsiloxane via three crosslinking agents, namely, tetraethoxysilane (TEOS), tetrapropoxysilane (TPOS), and polysilazane. Secondly, the ablation properties of RTV phenyl silicone rubber were studied by the muffle roaster test and FT-IR. Thirdly, thermal stability of the three samples was studied by thermogravimetric (TG) analysis. Finally, to explore the thermal degradation mechanism, the RTV phenyl silicone rubber vulcanized by different crosslinking agents were characterized by TG analysis-mass spectrum (TG-MS) and pyrolysis gas chromatogram-mass spectrum (pyGC-MS). Results showed that the thermal stability of RTV phenyl silicone rubber is related to the amount of residual Si⁻OH groups. The residual Si⁻OH groups initiated the polysiloxane chain degradation via an 'unzipping' mechanism.

Polymer Synthesis with More Than One Form of Living Polymerization Method.

Controlled radical polymerization (CRP) or controlled/living radical polymerization has revolutionized the polymer industry as a tool for the preparation of a wide variety of polymers. This process enables the preparation of polymers with good control of molecular weight, narrow polydispersity, and a range of architectures including block and graft copolymers, star polymers, and other functional polymers. The mechanistic transformation reaction provides a great opportunity to tune chemical and physical properties of copolymers. It can be applied to combine different homopolymers using post-modification techniques or by the use of a dual initiator, allowing the combination of mechanistically distinct polymerization reactions. This review will cover CRP transformations including the synthesis of block copolymers with both linear structures (AB, ABA, (AB) n , multiblocks, etc.) and branched macromolecular architectures (graft, miktoarm star, and dendritic-like), which are obtained by a combination of more than one form of living polymerization reaction.

Chain-Conformation-Directed Polymerization Cyclization for Effective Synthesis of Macrocycles in Bulk.

Biological cyclization is highly efficient, and this can be attributed to the conformation of the backbone of the biopolymer. Taking advantage of metal-coordination geometry, we developed a method for conformation-directed polymerization cyclization through rational design of metal carbonyl monomers that could be used to produce cyclic macromolecules, even in bulk. P FpR [P Fp=(PPh2 (CH2 )3 Cp)Fe(CO)2 with the phosphine group tethered on the cyclopentadiene (Cp) ring; R=CH3 or (CH2 )5 CH3 ] was designed and synthesized for migration insertion polymerization to generate P(P FpR) with the polymer backbone containing Cp-Fe bonds. Growth of the backbone led to a cyclic conformation with close end-to-end distances, which facilitated the cyclization. This conformation-directed cyclization was attributed to the piano-stool metal-coordination geometry of the repeating units and the low rotational barrier of the Cp-Fe bonds in the backbone. The produced macrocycles, which contain a metal carbonyl coordination structure in their backbones, are rigid, unlike many organic macrocycles. The macrocycles thus have a large excluded volume. This new type of metal carbonyl macrocycle will be of interest as a building block for supramolecular chemistry and in the exploration of novel materials.

Direct Synthesis of Polymer Nanotubes by Aqueous Dispersion Polymerization of a Cyclodextrin/Styrene Complex.

A one-step synthesis of nanotubes by RAFT dispersion polymerization of cyclodextrin/styrene (CD/St) complexes directly in water is presented. The resulted amphiphilic PEG-b-PS diblock copolymers self-assemble in situ into nanoparticles with various morphologies. Spheres, worms, lamellae, and nanotubes were controllably obtained. Because of the complexation, the swelling degree of polystyrene (PS) blocks by free St is limited, resulting in limited mobility of PS chains. Consequently, kinetically trapped lamellae and nanotubes were obtained instead of spherical vesicles. During the formation of nanotubes, small vesicles first formed at the ends of the tape-like lamellae, then grew and fused into nanotubes with a limited chain rearrangement. The introduction of a host-guest interaction based on CDs enables the aqueous dispersion polymerization of water-immiscible monomers, and produces kinetically trapped nanostructures, which could be a powerful technique for nanomaterials synthesis.

Polymeric Nanocarriers Based on Cyclodextrins for Drug Delivery: Host-Guest Interaction as Stimuli Responsive Linker.

Stimuli responsive polymers have been extensively studied as nanocarriers for drug delivery systems (DDSs), especially those based on supramolecular interactions. Cyclodextrin (CD) is one kind of widely applied host molecule, and the host-guest interactions between CD and different counterparts can respond to different stimuli and thus can be applied as responsive linkers for polymeric DDSs. In this review, the polymeric nanocarriers based on the host-guest interactions between CD and ferrocene, azobenzene, and benzimidazole as DDSs are summarized, with redox, light, and pH sensitivity, respectively. The mechanisms for the stimuli responsive ability of the linkers, the application of them for construction of DDSs with different polymer structures, and the controlled release behaviors have been focused. In addition, the outlook and challenge of these systems are discussed.

Electrochemical Stimulated Pickering Emulsion for Recycling of Enzyme in Biocatalysis.

Potential-stimulated Pickering emulsions, using electrochemical responsive microgels as particle stabilizers, are prepared and used for biocatalysis. The microgels are constructed from cyclodextrin functionalized 8-arm poly(ethylene glycol) (8A PEG-CD) and ferrocene modified counterparts (8A PEG-Fc) via CD/Fc host-guest chemistry. Taking advantage of the redox reaction of Fc, the formation and deformation of the microgels and corresponding Pickering emulsions can be reversibly stimulated by external potential, and have been used for the hydrolysis of triacetin and kinetic resolution reaction of (R,S)-1-phenylethanol catalyzed by lipases. Potential stimulated destabilization of the emulsion realizes an effective separation of the products and enzyme recycling.

CO2-breathing and piercing polymersomes as tunable and reversible nanocarriers.

Despite numerous studies on utilizing polymeric vesicles as nanocapsules, fabrication of tunable molecular pathways on transportable vesicle walls remains challenging. Traditional methods for building penetrated channels on vesicular membrane surface often involve regulating the solvent polarity or photo-cross-linking. Herein, we developed a neat, green approach of stimulation by using CO2 gas as "molecular drill" to pierce macroporous structures on the membrane of polymersomes. By simply introducing CO2/N2 gases into the aqueous solution of self-assemblies without accumulating any byproducts, we observed two processes of polymeric shape transformation: "gas breathing" and "gas piercing." Moreover, the pathways in terms of dimension and time were found to be adjustable simply by controlling the CO2 stimulation level for different functional encapsulated molecules in accumulation, transport, and releasing. CO2-breathing and piercing of polymersomes offers a promising functionality to tune nanocapsules for encapsulating and releasing fluorescent dyes and bioactive molecules in living systems and also a unique platform to mimic the structural formation of nucleus pore complex and the breathing process in human beings and animals.

Electrochemical Redox Switchable Dispersion of Single-Walled Carbon Nanotubes in Water.

We present a new, efficient approach to achieve superior dispersibility of single-walled carbon nanotubes (SWNTs) in water by integrating reversible host-guest interaction and π-π stacking. In this approach, ß-cyclodextrin (ß-CD) was first modified with a pyrene group to be adsorbed onto the wall of pristine SWNTs via π-π stacking, followed by further functionalization with ferrocene (Fc)-terminated water-soluble poly(ethylene glycol) (PEG) through supramolecular host-guest interaction between ß-CD and Fc. Upon alternate electrochemical oxidative/reductive stimuli, the reversible host-guest pair enabled the PEG-Fc@Py-CD@SWNTs to exhibit switchable conversion between dispersion and aggregation states. Electric field controllable PEG-Fc@Py-CD@SWNTs with good reversibility and intact nanotube structure may find potential applications in selective screening of SWNTs, biosensors, and targeted drug delivery.

Electrochemically-responsive magnetic nanoparticles for reversible protein adsorption.

Electrochemical stimulus is a clean and simple choice of stimulating source in the field of stimuli-responsive materials. Herein, we report an electrochemically-responsive hybrid assembly of magnetic nanoparticles (Fe3O4@SiO2-PGMA-CD) and polyethylene glycol-Fc (PEG-Fc) based on the host-guest interaction between ß-cyclodextrin and ferrocene groups. Through electrochemical control, the hydrophilic polymer chains can be reversibly linked to or dropped off from the surface of the magnetic nanoparticles. Thus, the hydrophobic property of the surface together with the protein adsorption ability of the magnetic nanoparticles can be conveniently adjusted by voltages applied. A reversible protein adsorption/release transition from this novel hybrid material has been realized, demonstrated by the bovine serum albumin adsorption experiment. Therefore, an elegant material is introduced to achieve electrochemically-controlled reversible magnetic separation of proteins.

Ferrocene-based supramolecular structures and their applications in electrochemical responsive systems.

Electrochemical stimuli have attracted much attention in recent years as they are simple, clean and can be widely applied in biological systems and material science. As one type of common guest molecules, ferrocene and its derivatives have been well studied with different host molecules, mainly including cyclodextrins, cucurbiturils, pillararenes and calixarenes. This article generally summarizes the recent work on the host-guest interactions between ferrocene derivatives and their host molecules, as well as various supramolecular systems based on these interactions. In addition, the development and outlook of electrochemical responsive systems are also discussed.