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This study introduces bis(1-cyanocyclohex-1-yl)trithiocarbonate (TTC-bCCH) as a novel trithiocarbonate chain transfer agent and compares its reactivity with the previously described bis(2-cyanopropan-2-yl)trithiocarbonate (TTC-bCP) for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St), n-butyl acrylate (nBA), and methyl methacrylate (MMA). Significant findings include the effective control of M n and low dispersities from the onset of polymerization of St and nBA showing swift addition-fragmentation kinetics, leading to similar behaviors between the two RAFT agents. In contrast, a fourfold decrease of the chain transfer constant to MMA is established for TTC-bCCH over TTC-bCP. This trend is confirmed through density functional theory (DFT) calculations. Finally, the study compares thermoplastic elastomer properties of all-(meth)acrylic ABA block copolymers produced with both RAFT agents. The impact of dispersity of PMMA blocks on thermomechanical properties evaluated via rheological analysis reveals a more pronounced temperature dependence of the storage modulus (G') for the triblock copolymer synthesized with TTC-bCCH, indicating potential alteration of the phase separation., (© 2024 The Author(s). Macromolecular Rapid Communications published by Wiley‐VCH GmbH.)

The creation of anisotropic nanostructures with precise size control is desirable for new properties and functions, but it is challenging for ionic self-assembly (ISA) because of the non-directional electrostatic interactions. Herein, the formation of size-controllable tetragonal nanoprisms is reported via crystallization-directed ionic self-assembly (CDISA) through evaporating a micellar solution on solid substrates. First, ISA is designed with a crystalline polyethylene oxide (PEO) containing cationic polymer poly(2-(2-guanidinoethoxy)ethyl methacrylate)-b-poly(ethyleneoxide)-b-poly(2-(2-guanidinoethoxy)-ethylmethacrylate) (PG n -PEO 230 -PG n ) and an anionic 5,10,15,20-Tetrakis(4-sulfonatophenyl) porphyrin (TPPS) to form micelles in aqueous solution. The PG segments binds excessive TPPS with amplenet chargeto form hydrophilic corona, while the PEO segments are unprecedentedly dehydrated and tightly packed into cores. Upon naturally drying the micellar solution on a silicon wafer, PEO crystallizationdirects the micelles to aggregate into square nanoplates, which are further connected to nanoprisms. Length and width of the nanoprisms can be facilely tuned by varying the initial concentration. In this hierarchical process, the aqueous self-assembly is prerequisite and the water evaporation rate is crucial for the formation of nanostructures, which provides multiple factors for morphology regulating. Such precise size-control strategy is highly expected to provide a new vision for the design of advanced materials with size controllable anisotropic nanostructures., (© 2023 Wiley-VCH GmbH.)

Inspired by the striated structure of skeletal muscle fibers, a polymeric actuator by assembling two symmetric triblock copolymers, namely, polystyrene-b-poly(acrylic acid)-b-polystyrene (SAS) and polystyrene-b-poly(ethylene oxide)-b-polystyrene (SES) is developed. Owing to the microphase separation of the triblock copolymers and hydrogen-bonding complexation of their middle segments, the SAS/SES assembly forms a lamellar structure with alternating vitrified S and hydrogen-bonded A/E association layers. The SAS/SES strip can be actuated and operate in response to environmental pH. The contraction ratio and working density of the SAS/SES actuator are approximately 50% and 90 kJ m -3 , respectively; these values are higher than those of skeletal muscle fibers. In addition, the SAS/SES actuator shows a "catch-state", that is, it can maintain force without energy consumption, which is a feature of mollusc muscle but not skeletal muscle. This study provides a biomimetic approach for the development of artificial polymeric actuators with outstanding performance., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Associations of amphiphiles assume their various morphologies according to the so-called packing parameter under thermodynamic control. However, one may raise the question of whether polymers can always relax fast enough to obey thermodynamic control, and how this may be checked. Here, a case of polyion complex (PIC) assemblies where the morphology appears to be subject to kinetic control is discussed. Poly (ethylene oxide)-b-(styrene sulfonate) block copolymers are combined with cationic PAMAM dendrimers of various generations (2-7). The PEO-PSS diblocks, and the corresponding PSS-PEO-PSS triblocks should have nearly identical packing parameters, but surprisingly creat different assemblies, namely core-shell micelles and vesicles, respectively. Moreover, the micelles are very stable against added salt, whereas the vesicles are not only much more sensitive to added salt, but also appear to exchange matter on relevant time scales. The small and largely quenched early-stage precursor complexes are responsible for the morphological and dynamic differences, implying that kinetic control may also be a way to obtain particles with well-defined and useful properties. The exciting new finding that triblocks produce more "active" vesicles will hopefully trigger the exploration of more pathways, and so learn how to tune PICsomes toward specific applications., (© 2021 Wiley-VCH GmbH.)

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 CO 2 /O 2 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., (© 2021 Wiley-VCH GmbH.)

Recent years have seen an increased interest in the use of ABC triblock terpolymers to bottom-up assemble multicompartment patchy nanoparticles. Despite these experimental and theoretical efforts, the applications of polymer-based patchy nanoparticles remain rather limited. One of the major challenges that eclipses their potential is the lack of knowledge to selectively encapsulate cargoes within different compartments that are separated in the nanometer length scale. Here, strategies are reported to segregate two chemically distinct molecules in either the patches or core compartment of patchy nanoparticles that bear a (bioactive) sugar corona. The potential use of these bioactive patchy nanoparticles containing compartmentalized cargoes for simultaneous drug delivery with real-time release monitoring capabilities is further demonstrated., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Well-defined β-cyclodextrin (β-CD)-terminated double hydrophilic diblock copolymers (DHBCs), β-CD- poly(di(ethylene glycol) methyl ether methacrylate) (PMEO 2 MA)-b-poly(2-(diethylamino)ethyl methacrylate) (PDEA) (BP1) and β-CD-PDEA-b-PMEO 2 MA (BP2), are synthesized via sequential atom transfer radical polymerizations of di(ethylene glycol) methyl ether methacrylate and 2-(diethylamino)ethyl methacrylate using alkynyl-functionalized initiator, followed by click reactions with an excess of mono-azido-substituted β-cyclodextrin (β-CD-N 3 ). The micellization behavior of these as-prepared DHBCs in aqueous solutions suffers from insufficient colloidal stabilities at basic pH and high temperatures (e.g., pH 9 and 45 °C), resulting in the formation of macroscopic precipitations. However, the stabilities of colloidal nanoparticles can be remarkably enhanced as a result of the convenient formation of three-layered micelles by taking advantage of host-guest interactions of BP1/BP2 and Ad-terminated poly(ethylene glycol). The pH- and thermoresponsive three-layered micelles with enhanced stability may augur promising applications in targeted drug delivery and controlled intelligent release., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Template-free fabrication of non-spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self-assembly from aqueous solutions at room temperature. Nanocubes with edges of 40-200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self-assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solid cubic particle formation. An approach for preserving the structures of these cubes in water by thiol- or photo-induced crosslinking was developed. The ability to solubilize a model hydrophobic drug, curcumin, was also explored., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene)., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The coupling of hollow carbon nanospheres with triblock copolymers is a promising strategy to fabricate mixed-matrix membranes. This is because the symmetric microporous shells combine with the hollow space to promote gas transport, and the unique soft-rigid molecular structure of triblock copolymers can accommodate a high loading of fillers without a significant loss of mechanical strength., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The preparation of physically crosslinked hydrogels from quasi ABA-triblock copolymers with a water-soluble middle block and hydrophobic end groups is reported. The hydrophilic monomer N-acryloylmorpholine is copolymerized with hydrophobic isobornyl acrylate via a one-pot sequential monomer addition through reversible addition fragmentation chain-transfer (RAFT) polymerization in an automated parallel synthesizer, allowing systematic variation of polymer chain length and hydrophobic-hydrophilic ratio. Hydrophobic interactions between the outer blocks cause them to phase-separate into larger hydrophobic domains in water, forming physical crosslinks between the polymers. The resulting hydrogels are studied using rheology and their self-healing ability after large strain damage is shown., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Self-assembly of block copolymers provides numerous opportunities to create functional materials, utilizing self-assembled microdomains with a variety of morphology and periodic architectures as templates for functional nanofillers. Here new progress is reported toward the fabrication of thermally responsive and electrically conductive polymeric self-assemblies made from a water-soluble poly(thiophene) derivative with short poly(ethylene oxide) side chains and Pluronic L62 block copolymer solution in water. The structural and electrical properties of conjugated polymer-embedded self-assembled architectures are investigated by combining small-angle neutron and X-ray scattering, coarse-grained molecular dynamics simulations, and impedance spectroscopy. The L62 solution template organizes the conjugated polymers by stably incorporating them into the hydrophilic domains thus inhibiting aggregation. The changing morphology of L62 during the micellar-to-lamellar phase transition defines the embedded conjugated polymer network. As a result, the conductivity is strongly coupled to the structural change of the templating L62 phase and exhibits thermally reversible behavior with no signs of quenching of the conductivity at high temperature. This study shows promise for enabling more flexibility in processing and utilizing water-soluble conjugated polymers in aqueous solutions for self-assembly based fabrication of stimuli-responsive nanostructures and sensory materials., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Ethylene-propylene-methyl methacrylate (MMA) and ethylene-hexene-MMA A-B-C block copolymers with high molecular weight (>100,000) are synthesized using fluorenylamide-ligated titanium complex activated by modified methylaluminoxane and 2,6-di-tert-butyl-4-methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Star-like amphiphilic triblock copolymers were rationally designed and synthesized by combining two sequential atom-transfer radical polymerization reactions with a click reaction. Subsequently, a family of uniform magnetic/plasmonic core/shell nanoparticles was crafted by capitalizing on these triblock copolymers as nanoreactors. The diameter of the magnetic core and the thickness of the plasmonic shell could be independently and accurately controlled by varying the molecular weights (i.e., the chain lengths) of the inner and intermediate blocks of the star-like triblock copolymers, respectively. The surface plasmonic absorption of core/shell nanoparticles with different core diameters and shell thicknesses was systematically studied and theoretically modeled. This robust strategy provides easy access to a large variety of multifunctional nanoparticles with large lattice mismatches for use in optics, optoelectronics, catalysis, or bioimaging., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis of triblock copolymers based on polysarcosine, poly-N-ε-t-butyloxycarbonyl-l-lysine, and poly-N-ε-t-trifluoroacetyl-l-lysine by ring-opening polymerization of the corresponding α-amino acid N-carboxyanhydrides (NCAs) is described. For the synthesis of N-ε-t-butyloxycarbonyl-l-lysine (lysine(Boc)) NCAs, an acid-free method using trimethylsilylchloride/triethylamine as hydrochloric acid (HCl) scavengers is presented. This approach enables the synthesis of lysine(Boc) NCA of high purity (melting point 138.3 °C) in high yields. For triblock copolypept(o)ides, the degree of polymerization (Xn ) of the polysarcosine block is varied between 200 and 600; poly-N-ε-t-butyloxycarbonyl-l-lysine and poly-N-ε-t-trifluoroacetyl-l-lysine blocks are designed to have a Xn in the range of 10-50. The polypeptide-polypeptoid hybrids (polypept(o)ides) can be synthesized with precise control of molecular weight, high end group integrity, and dispersities indices between 1.1 and 1.2. But more important, the use of tert-butyloxycarbonyl- and trifluoroacetyl-protecting groups allows the selective, orthogonal deprotection of both blocks, which enables further postpolymerization modification reactions in a block-selective manner. Therefore, the presented synthetic approach provides a versatile pathway to triblock copolypept(o)ides, in which functionalities can be separated in specific blocks., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)