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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 Mn 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. [ABSTRACT FROM AUTHOR]

Supramolecular polymer networks (SPNs) have attracted much research attention due to their good performance in the preparation of adaptive materials. Controlling the distribution of supramolecular interactions in the networks is a good strategy to tune the properties of SPNs, but corresponding study is still rare. Herein, we construct two triblock copolymers in ABA and BAB forms to control the supramolecular interaction concentrated in A block, leading to two SPNs with divergent mechanical performances. In specific, the SPN-1 formed by ABA triblock copolymer displays a slightly and densely distributed hard domain and a compact network, resulting in a decent toughness. While the SPN-2 composed of BAB triblock copolymer is rigid and less elastic, whose microphase-separated structures are more obvious, making the network difficult to withstand larger strains. These findings are conducive to deepening the understanding of SPNs and would promote the development of supramolecular block copolymers with emergent functions and applications. [ABSTRACT FROM AUTHOR]

The development of composite materials with thermo-optical properties based on smart polymeric systems and nanostructures have been extensively studied. Due to the fact of its ability to self-assemble into a structure that generates a significant change in the refractive index, one of most attractive thermo-responsive polymers is poly(N-isopropylacrylamide) (PNIPAM), as well as its derivatives such as multiblock copolymers. In this work, symmetric triblock copolymers of polyacrylamide (PAM) and PNIPAM (PAMx-b-PNIPAMy-b-PAMx) with different block lengths were prepared by reversible addition−fragmentation chain-transfer polymerization (RAFT). The ABA sequence of these triblock copolymers was obtained in only two steps using a symmetrical trithiocarbonate as a transfer agent. The copolymers were combined with gold nanoparticles (AuNPs) to prepare nanocomposite materials with tunable optical properties. The results show that copolymers behave differently in solution due to the fact of variations in their composition. Therefore, they have a different impact on the nanoparticle formation process. Likewise, as expected, an increase in the length of the PNIPAM block promotes a better thermo-optical response. [ABSTRACT FROM AUTHOR]

Biodegradable poly(ε -caprolactone-co-lactide)- b -poly(ethylene glycol)- b -poly(ε -caprolactone- co -lactide) (PCLA-PEG-PCLA) triblock copolymer was developed to prepare thermosensitive inks for digital fiber printing applications. The thermosensitive inks can be printed on any textile or fiber that does not need to go through the pretreatment and soaping procedure like traditional inks. This copolymer aqueous solution has a reversible sol–gel transition property, which can be used to prepare thermosensitive sol–gel inks. PCLA-PEG-PCLA had little effect on the physical properties of the inks, including the average particle size, conductivity, and surface tension at room temperature. However, the viscosity of the thermosensitive inks can increase dramatically under high temperature. This was due to the inks undergoing a sol–gel transition with an increase of temperature. The inks were in the sol state in the printer cartridge at room temperature and when the ink drops fell on the heated fiber or textile, a sol–gel transition occurred and turned them into a gel immediately. The high viscosity prevented the ink from spreading around on the fabrics, thus giving a sharp edge. The study indicated that the line width printed by thermosensitive inks was reduced to 266.35 μm from 464.08 μm in the weft direction (reduced by 43%), and the line width in the warp direction was reduced to 264.35 μm from 385.76 μm (reduced by 32%). The polyester fabric printed by thermosensitive ink has a higher color strength (K / S) at 47–50°C with excellent colorfastness. Thermosensitive ink is a type of innovative ink, in line with the concept of green ecological textile manufacturing. [ABSTRACT FROM AUTHOR]

New biodegradable aliphatic PLLA-PBA-PLLA copolymers with soft poly(butylene adipate) (PBA) and hard poly(l-lactide) (PLLA) building blocks were synthesized via ring-opening polymerization (ROP). Proton nuclear magnetic resonance (1HNMR) was utilized to confirm the volume fraction of PBA (fPBA) within PLLA-PBA-PLLA. It was found that a PBA midblock (PBA-mid) within PLLA-PBA-PLLA-s (PLLA-PBA-PLLA triblock copolymer with a short PLLA block length) might display lamellar domain structure. However, PBA-mid within PLLA-PBA-PLLA-l (PLLA-PBA-PLLA triblock copolymer with a long PLLA block length) might locate itself as a nanoscale cylindrical domain surrounded by a PLLA continuous phase. Polymorphic crystals of PBA-mid within the PLLA-PBA-PLLA copolymers were formed after melt crystallization at the given temperatures, which were studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis. According to the WAXD and DSC analyses, it was interesting to find that the α-type crystal of PBA-mid was favorable to develop in the lower temperature region regardless of the state (crystallization or amorphous) of the PLLA component. Additionally, when the PLLA component was held in its amorphous state, it was easier for PBA-mid within the PLLA-PBA-PLLA copolymers to transform from the metastable β-form crystal to the stable α-form crystal. Furthermore, polarized optical microscopy (POM) photos provided direct evidence of the polymorphic crystals of PBA-mid within PLLA-PBA-PLLAs. [ABSTRACT FROM AUTHOR]

Leishmaniases are neglected tropical diseases caused by obligate intracellular protozoa of the genus Leishmania. The drugs used in treatment have a high financial cost, a long treatment time, high toxicity, and variable efficacy. 3-Carene (3CR) is a hydrocarbon monoterpene that has shown in vitro activity against some Leishmania species; however, it has low water solubility and high volatility. This study aimed to develop Poloxamer 407 micelles capable of delivering 3CR (P407-3CR) to improve antileishmanial activity. The micelles formulated presented nanometric size, medium or low polydispersity, and Newtonian fluid rheological behavior. 3CR and P407-3CR inhibited the growth of L. (L.) amazonensis promastigote with IC50/48h of 488.1 ± 3.7 and 419.9 ±1.5 mM, respectively. Transmission electron microscopy analysis showed that 3CR induces multiple nuclei and kinetoplast phenotypes and the formation of numerous cytosolic invaginations. Additionally, the micelles were not cytotoxic to L929 cells or murine peritoneal macrophages, presenting activity on intracellular amastigotes. P407-3CR micelles (IC50/72 h = 0.7 ± 0.1 mM) increased the monoterpene activity by at least twice (3CR: IC50/72 h >1.5 mM). These results showed that P407 micelles are an effective nanosystem for delivering 3CR and potentiating antileishmanial activity. More studies are needed to evaluate this system as a potential therapeutic option for leishmaniases.

The development of composite materials with thermo-optical properties based on smart polymeric systems and nanostructures have been extensively studied. Due to the fact of its ability to self-assemble into a structure that generates a significant change in the refractive index, one of most attractive thermo-responsive polymers is poly(N-isopropylacrylamide) (PNIPAM), as well as its derivatives such as multiblock copolymers. In this work, symmetric triblock copolymers of polyacrylamide (PAM) and PNIPAM (PAMx-b-PNIPAMy-b-PAMx) with different block lengths were prepared by reversible addition−fragmentation chain-transfer polymerization (RAFT). The ABA sequence of these triblock copolymers was obtained in only two steps using a symmetrical trithiocarbonate as a transfer agent. The copolymers were combined with gold nanoparticles (AuNPs) to prepare nanocomposite materials with tunable optical properties. The results show that copolymers behave differently in solution due to the fact of variations in their composition. Therefore, they have a different impact on the nanoparticle formation process. Likewise, as expected, an increase in the length of the PNIPAM block promotes a better thermo-optical response.

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. [ABSTRACT FROM AUTHOR]

The interactions of egg yolk phosphatidylcholine liposomes with F108 and F127 triblock copolymers, in the monomer state, were analyzed by isothermal titration calorimetry (ITC) at 37 °C. According to the results, the critical micelle concentration was determined to be 0.4 and 0.04 wt.% for F108 and F127, respectively, by surface tension at 37 °C. According to the results, liposomes/poloxamers were not favoured energetically, since endothermic interactions were observed. However, positive changes in entropy promoted a spontaneous process. F127 had a greater partition coefficient (51.97 ± 1.77 × 104), stronger affinity, than F108 (8.19 ± 0.37 × 104) towards the vesicle lipid bilayer due to its larger hydrophobic block. After the ITC experiments, an increased vesicle size (within about 1–3 nm average) by dynamic light scattering and the formation of bilayer discs by electron microscopy (EM) was observed at low copolymer concentrations (0.57 mol% of F108 and 1.01 mol% of F127). The EM and ITC results confirmed the intimate association of the copolymers with the membrane instead of being simply absorbed onto the bilayer surface. Our results indicate that the temperature of the system (37 °C), the copolymer concentration and hydrophobic chain length are important factors for the interaction of poloxamers with lipid bilayers and the stability of liposomes. [ABSTRACT FROM AUTHOR]

Abstract 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.

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. [ABSTRACT FROM AUTHOR]

Surface‐initiated polymerization of various monomers (methacrylic acid, methacrylate, acrylate, acrylamide, and zwitterionic monomer) is conducted to form triblock copolymer brushes using oxygen‐initiated reversible addition−fragmentation chain‐transfer polymerization in the presence of air. An ellipsometry analysis, water contact angle analysis, X‐ray photoelectron spectroscopy, and atomic force microscopy confirm the successful formation of polymer brushes with complex architectures on a silicon substrate. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

New biodegradable aliphatic PLLA-PBA-PLLA copolymers with soft poly(butylene adipate) (PBA) and hard poly(l-lactide) (PLLA) building blocks were synthesized via ring-opening polymerization (ROP). Proton nuclear magnetic resonance (1HNMR) was utilized to confirm the volume fraction of PBA (fPBA) within PLLA-PBA-PLLA. It was found that a PBA midblock (PBA-mid) within PLLA-PBA-PLLA-s (PLLA-PBA-PLLA triblock copolymer with a short PLLA block length) might display lamellar domain structure. However, PBA-mid within PLLA-PBA-PLLA-l (PLLA-PBA-PLLA triblock copolymer with a long PLLA block length) might locate itself as a nanoscale cylindrical domain surrounded by a PLLA continuous phase. Polymorphic crystals of PBA-mid within the PLLA-PBA-PLLA copolymers were formed after melt crystallization at the given temperatures, which were studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis. According to the WAXD and DSC analyses, it was interesting to find that the α-type crystal of PBA-mid was favorable to develop in the lower temperature region regardless of the state (crystallization or amorphous) of the PLLA component. Additionally, when the PLLA component was held in its amorphous state, it was easier for PBA-mid within the PLLA-PBA-PLLA copolymers to transform from the metastable β-form crystal to the stable α-form crystal. Furthermore, polarized optical microscopy (POM) photos provided direct evidence of the polymorphic crystals of PBA-mid within PLLA-PBA-PLLAs.

Despite the outstanding role of mesoscopic structures on the efficiency and stability of perovskite solar cells (PSCs) in the regular (n–i–p) architecture, mesoscopic PSCs in inverted (p–i–n) architecture have rarely been reported. Herein, an efficient and stable mesoscopic NiOx (mp‐NiOx) scaffold formed via a simple and low‐cost triblock copolymer template‐assisted strategy is employed, and this mp‐NiOx film is utilized as a hole transport layer (HTL) in PSCs, for the first time. Promisingly, this approach allows the fabrication of homogenous, crack‐free, and robust 150 nm thick mp‐NiOx HTLs through a facile chemical approach. Such a high‐quality templated mp‐NiOx structure promotes the growth of the perovskite film yielding better surface coverage and enlarged grains. These desired structural and morphological features effectively translate into improved charge extraction, accelerated charge transportation, and suppressed trap‐assisted recombination. Ultimately, a considerable efficiency of 20.2% is achieved with negligible hysteresis which is among the highest efficiencies for mp‐NiOx based inverted PSCs so far. Moreover, mesoscopic devices indicate higher long‐term stability under ambient conditions compared to planar devices. Overall, these results may set new benchmarks in terms of performance for mesoscopic inverted PSCs employing templated mp‐NiOx films as highly efficient, stable, and easy fabricated HTLs. [ABSTRACT FROM AUTHOR]

This study describes the synthesis and characterization of triblock copolymers composed of poly[2-(methacryloyloxy)ethyl phosphorylcholine]- block -poly(propylene glycol)- block -poly[2-(methacryloyloxy)ethyl phosphorylcholine] (PMPC- b -PPG- b -PMPC) intended for, but not limited to, applications in colloidal drug delivery. Atom transfer radical polymerization led to a library of well-defined PMPC- b -PPG- b -PMPC triblock copolymers with varying overall molecular weight (ranging from ∼5 to ∼25 kDa) and composition (weight fraction of the hydrophobic PPG block ranged from ∼10 to ∼50 wt%). The properties of the synthesized triblock copolymers were linked to the PPG to bioinspired PMPC block(s) ratio, where the more hydrophilic species showed adequate aqueous solubility, surface activity and biocompatibility (non-toxicity) in in vitro cell culture. Their amphiphilic nature makes them adsorb efficiently onto polymer nanoparticles, what improves colloidal stability under stress conditions and, furthermore, depletes proteins from unwanted adsorption to the underlying surface. The current findings strengthen our insights into structure-function relationships of PMPC-based coatings leading to protecting shells on relevant polymer nanoparticle formulations. PMPC- b -PPG- b -PMPC triblock copolymers composed of a hydrophobic PPG block of 2–4 kDa flanked by two hydrophilic PMPC blocks each of 5–10 kDa seem to be most promising to enhance colloidal drug delivery vehicles. [Display omitted] • Bioinspired copolymers were challenged for their applicability in nanomedicine. • Hydrophilic polymers showed adequate biocompatibility and improved nanoparticle properties. • Structure-function relationships with relevance for nanomedicine are disclosed. [ABSTRACT FROM AUTHOR]

Nitrile oxide 1,3 dipolar cycloaddition is a simple and powerful coupling methodology. However, the self-dimerization of nitrile oxides has prevented the widespread use of this strategy for macromolecular coupling. By combining an in situ nitrile oxide generation with a highly reactive activated dipolarophile, we have overcome these obstacles and present a metal-free macromolecular coupling strategy for the modular synthesis of several ABA triblock copolymers. Nitrile oxides were generated in situ from chloroxime terminated poly(dimethylsiloxane) B-blocks and coupled with several distinct hydrophilic (poly(2-methyloxazoline) and poly(ethylene glycol)), and poly(N-isopropylacrylamide) or hydrophobic (poly(L-lactide) A-blocks terminated in activated dipolarophiles in a rapid fashion with high yield. This methodology overcomes many drawbacks of previously reported metal-free methods due to its rapid kinetics, versatility, scalability, and ease of introduction of necessary functionality. Nitrile oxide cycloaddition should find use as an attractive macromolecular coupling strategy for the synthesis of biocompatible polymeric nanostructures.

A triblock copolymer with hydrophobic end blocks and a polyampholytic middle block is investigated in a mixture of water and acetone with a focus on the dependence of the rheological properties and of the micellar structure and correlation on the content of acetone. The polymer under study is PMMA86-b-P(DEA190-co-MAA96)-b-PMMA86, where PMMA stands for poly(methyl methacrylate) and P(DEA-co-MAA) for poly(2-(diethylamino) ethyl methacrylate-co-methacrylic acid). The pH is chosen at 3. Rheological measurements reveal a transition from a viscoelastic solid over a viscoelastic liquid to a freely flowing liquid upon addition of 5 or 10 wt% of acetone to a 3 wt% aqueous polymer solution, respectively. Using small-angle neutron scattering on 0.5 wt% polymer solutions in water/acetone with the content of the latter ranging between 0 and 30 wt%, significant structural changes are observed as well, such as a decrease of the distance between the PMMA cross-links and of the size of the network clusters upon increasing acetone constant. These changes are attributed to the reduction of the dielectric constant by the addition of the cosolvent acetone, enhancing the flexibility of the middle blocks and their tendency to backfolding, as well as to the decrease of the solvent selectivity, inducing significant exchange rate enhancement of the core-forming PMMA blocks. [ABSTRACT FROM AUTHOR]

• Forces between silica surfaces in Pluronic solutions with NaCl were measured by AFM. • Below CMC, the interactions were steric repulsion when NaCl concentration was low. • High NaCl concentration brought bridging attraction below CMC. • Above CMC, the interactions were steric repulsion caused by adsorbed micelle layers. • The length of the PEO group was found to affect considerably on the interactions. Triblock copolymers composed of polyethylene oxide (PEO) and polypropylene oxide (PPO) are used in various fields as nonionic surfactants. In this study, we measured interaction forces between untreated hydrophilic silica surfaces in solutions with two typical triblock copolymers, Pluronic P123 (PEO 20 PPO 70 PEO 20) and F127 (PEO 99 PPO 65 PEO 99), in the presence of 1 mM and 500 mM NaCl using atomic force microscopy (AFM). In solutions at the copolymer concentration of 1 µM, which is below the critical micelle concentration (CMC), the measured interaction forces were monotonically repulsive in the presence of 1 mM NaCl, which suggested the brush-like conformation of copolymers on the surfaces. When the concentration of NaCl was increased to 500 mM, interaction forces became attractive, which indicated the bridging of adsorbed polymers onto surfaces, the strength of which varied depending on the affinity and adsorption density of copolymers. The interactions at the copolymer concentration of 1 mM, which were above the CMC of both copolymers, were steric repulsions between adsorbed micelles on the surfaces with 1 mM of NaCl. For 500 mM of NaCl, an attractive jump after a steric repulsion was observed only in the force curve for P123, which inferred that the displacement of micelles from the surfaces was presumably due to a decrease in the strength of adsorption caused by the dehydration of EO groups. These results indicated that the length of the EO group considerably affected the interactions. [ABSTRACT FROM AUTHOR]

A novel biodegradable amphiphilic triblock copolymer, polyphosphate, polyethylene glycol, and polylactic acid (PAEEP-PEG-PLLA), was synthesized by twice ring-opening polymerization and triphenylphosphine (TPP) was grafted onto the block copolymer to synthesize a carrier material TPP-PAEEP-PEG-PLLA, which was identified by 1 H-nuclear magnetic resonance ( 1 H-NMR) spectroscopy. The TPP-PAEEP-PEG-PLLA nanoparticles encapsulated with ursolic acid (UA) were prepared by the emulsion-solvent evaporation method and characterized by dynamic light scattering. The mitochondrial targeting ability of fluorescently labeled nanoparticles was evaluated by laser confocal microscopy. The average particle size and surface charge of the UA -loaded nanoparticle solution were 180.07 ± 1.67 nm and +15.57 ± 1.33 mV, respectively. The biocompatibility of nanoparticles was briefly evaluated by erythrocyte hemolysis assay. In vitro cell proliferation assay and scratch migration assay were performed to compare the difference in anti-tumor effect between UA and UA nanoparticles. The results showed that TPP-modified triblock copolymers had good mitochondrial targeting and improved the low bioavailability of UA, and UA nanoparticles exhibited more pronounced anti-tumor capabilities. In summary, the results suggested that our UA nanoparticles were a promising drug-targeted delivery system for the treatment of tumors., (© 2024 IOP Publishing Ltd.)

In recent years, nanotechnology has been a strong ally to Medicinal Chemistry. Liposomes stand out, being cell membrane models and excellent biocompatible drug delivery systems. However, liposomes have limitations due to their low stability in solutions and rapid elimination from the blood stream. These factors prevent the accumulation of these structures in tumor tissues, as well as the effects of permeability and retention (EPR effect). Given this scenario, several strategies have been developed aiming toincrease the stability and the circulation of liposome in the blood stream. Recent research has shown that surface-modified liposomes with polyethylene glycol (PEG), triblock ABA-like copolymers or site-specific ligands are able to overcome these issues. With that in mind, this article brings a review of the main scientific contributions in the development, optimization and improvement of liposomes as long circulation systems aiming at new strategies for drug formulation in cancer treatment.

We perform a comprehensive Monte Carlo study of the ABA triblock self-assembly by the Cooperative Motion Algorithm. Our attention is focused on three series of triblocks which are grown from parent AB diblocks of varying asymmetry. Unlike the previous studies in which the total length of the chain varies upon growing the terminal A-block, here we keep the fixed chain length for a given series. Moreover, we determine the order-disorder transition temperature as the parameter (being the ratio of the grown A-block to the length of the parent diblock) increases. In this case we find that the order-disorder transition temperature monotonically decreases for two asymmetric series which is different from the non-monotonic depression of TODT reported previously. We also construct a phase diagram which shows a variety of nanostructures as is increased. [ABSTRACT FROM AUTHOR]

ABA and BAB triblock amphiphilic copolymers based on sucrose methacrylate and methyl methacrylate are synthesized by sequential reversible addition–fragmentation chain transfer polymerization using S,S′‐bis(R,R′‐dimethyl‐R′′‐acetic acid)‐trithiocarbonate as a chain transfer agent. The copolymers present narrow molar mass dispersity, controlled molar mass and architecture as determined by gel permeation chromatography and 1H and 13C nuclear magnetic resonance. The copolymers with molar and mass fractions of poly(sucrose methacrylate) block ranging from 1 to 22 mol% and 3 to 52 wt%, respectively, and different molar masses present characteristics of a surfactant such as self‐assembly. The self‐assembly of the triblock copolymers in water, N,N‐dimethylformamide (DMF), dichloromethane, tetrahydrofuran, or benzene results mostly in vesicles as confirmed by scanning electron microscopy images and small‐angle X‐ray of the dispersions. Moreover, the copolymers present the capability to stabilize aromatic molecules (Nile Red dye) and nonpolar solvents in an aqueous phase and polar ionic molecules (methylene blue) and water in a nonpolar medium, suggesting the potential for application in drug encapsulation, environmental remediation systems, and molecular extraction in liquid–liquid immiscible systems, for example. Films prepared by casting from copolymer solutions in DMF present a lamellar structure with the lamellar thickness varying according to the copolymer molar mass. [ABSTRACT FROM AUTHOR]

The poly(l -lactide-b-ethylene glycol-b- l -lactide) (PLLA-PEG-PLLA) triblock copolymers with different chain segment length are fabricated by ring-opening polymerization. The structure, molecular weight, and crystallization behaviors of the triblock copolymers are characterized by Fourier transform infrared, nuclear magnetic resonance spectroscopy, gel permeation in chromatography, X-ray diffraction, differential scanning calorimetry, and polarizing optical microscopy (POM). The results show that the increase of block length is beneficial to improve its crystallization. In addition, the triblock copolymer exhibits a double crystallization phenomenon. The POM results indicate that PEG and PLLA chains of the copolymer crystallize in their respective crystallization temperature regions. The growth rate of the PLLA spherocrystal decreases and the dendritic spherocrystals appear with increasing the PEG chain length when the PLLA chain of the copolymer is isothermal crystallized at 80°C and PLLA chain length is constant. The growth rate of the PEG spherocrystal decreases and the spherocrystal morphology changes little with increasing PLLA chain length when the PEG chain is isothermal crystallized at 25°C and the length of PEG chain remained unchanged. [ABSTRACT FROM AUTHOR]

Mechanical properties including the failure behavior of physically assembled gels or physical gels are governed by their network structure. To investigate such behavior, we consider a physical gel system consisting of poly(styrene)‐poly(isoprene)‐poly(styrene)[PS‐PI‐PS] in mineral oil. In these gels, the endblock (PS) molecular weights are not significantly different, whereas, the midblock (PI) molecular weight has been varied such that we can access gels with and without midblock entanglement. Small angle X‐ray scattering data reveals that the gels are composed of collapsed PS aggregates connected by PI chains. The gelation temperature has been found to be a function of the endblock concentration. Tensile tests display stretch‐rate dependent modulus at high strain for the gels with midblock entanglement. Creep failure behavior has also been found to be influenced by the entanglement. Fracture experiments with predefined cracks show that the energy release rate scales linearly with the crack‐tip velocity for all gels considered here. In addition, increase of midblock chain length resulted in higher viscous dissipation leading to a higher energy release rate. The results provide an insight into how midblock entanglement can possibly affect the mechanical properties of physically assembled triblock copolymer gels in a midblock selective solvent. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1014–1026 [ABSTRACT FROM AUTHOR]

To develop carbon dioxide-reducible polymeric materials, triblock copolymers (PLA-polyester-PLA) of enantiomeric lactides and biopolyester diol, were synthesized by the ring-opening polymerization of lactide in the presence of diol using stannous octoate. The results showed that the incorporation of the biopolyester decreases the crystallinity and melting temperature of PLA. However, the blend of enantiomeric PLA copolymers revealed more thermal stability than homo- and copolymers. It was due to the formation of stereocomplexes between enantiomeric PLAs. The topographic images of degradation showed that the degradation rate of a copolymer was faster than of PLA while that of stereocomplex became much slower. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In order to create a new drug delivery system, the ibuprofen-loaded triblock copolymer PCL/PEO/PCL (PCEC) microspheres with a low PEO content (<2 wt%) were prepared by oil in water (o/w) solvent evaporation technique. The influence of PEO content, molecular weight of a polymer matrix and drug loading on the ibuprofen release profiles were evaluated. The interactions between polymer matrix and ibuprofen were detected by FTIR analysis. The presence of hydrophilic PEO segment in PCL chains caused the decrease in particle size, which further had a great impact on the drug release kinetics, i.e., initially faster release and significantly higher quantity of released drug compared to neat PCL. Ibuprofen release behavior from polymer matrix was governed by a diffusion process. In vitro cytotoxicity tests revealed that empty PCL and PCEC microspheres were not toxic at low concentrations, while ibuprofen-loaded microspheres exhibited cytotoxicity correlated with amounts of incorporated drug. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Fatty acid-based triblock copolymers with a transient network were synthesized. • Acrylamide, a hydrogen bonding comonomer, was copolymerized into the midblock. • Mechanical properties were significantly improved due to the transient network. • Order-disorder transition temperature decreased, providing enhanced processability. • Negligible impact of acrylamide comonomer on triblock copolymer morphology. Abstract Vegetable oils and their fatty acids are convenient sources for polymers due to their wide availability, ease of functionalization, and lack of toxicity; however, the long alkyl chains of the fatty acids have a large impact on the resulting polymer properties. Polymers with bulky constituents, such as the long alkyl side-chains of fatty acid-derived polymers, typically exhibit poor mechanical performance due to lack of entanglements. In this study, hydrogen bonding moieties were incorporated into the fatty acid-based midblock of a thermoplastic elastomeric triblock copolymer as a means to improve its mechanical behavior. Poly(styrene- b -(lauryl acrylate- co -acrylamide)- b -styrene), containing lauryl acrylate (a derivative of lauric acid) and the hydrogen bonding comonomer acrylamide in the midblock, was synthesized via reversible addition-fragmentation chain transfer polymerization. The chemical and physical properties of triblock copolymers of varying composition were explored. Quantitative FTIR analysis confirmed the formation of a transient network, which exhibited a reduction in crosslink density with increasing temperature, beneficial for high temperature melt processing. The triblock copolymers exhibited spherical morphologies lacking long-range order at room temperature, which were unaffected by the presence of acrylamide. Moreover, the order-disorder transition temperature reduced with increasing acrylamide content, due to a reduction in the Flory-Huggins interaction parameter. Importantly, incorporation of acrylamide into the midblock greatly improved both the tensile strength and strain at break. Incorporation of a transient network into the midblock is therefore an effective method of improving the mechanical properties of triblock copolymer-based thermoplastic elastomers containing bulky constituents. [ABSTRACT FROM AUTHOR]

Three different ABA‐type triblock copolymers each containing biodegradable aliphatic polycarbonate as the middle block and poly(l‐lactide) as the outer blocks were synthesized and the influence of the methylene chain length of the aliphatic polycarbonate middle block on various properties of the triblock copolymers was evaluated. Differential scanning calorimetry and wide‐angle X‐ray diffraction studies revealed that the incorporation of the outer blocks reduced the crystallinity of the middle aliphatic polycarbonate block. Variation of methylene chain length of the middle block led to a change in morphology from spherical to cylindrical as evidenced from atomic force microscopy studies. In addition, the mechanical properties of the block copolymers showed semi‐ductile to quasi‐brittle behaviour depending upon the composition of the middle block which was also confirmed using scanning electron microscopy. Dynamic mechanical analysis of the triblock copolymers indicated that storage modulus increased with a decrease in methylene chain length. © 2018 Society of Chemical Industry This study demonstrates that by changing the aliphatic polycarbonate middle block of a triblock copolymer, the morphology and mechanical properties of the triblock copolymer can be tailored. [ABSTRACT FROM AUTHOR]

The effect of different polyoxyethylene–polyoxypropylene triblock copolymers, their concentration, and mode of action on the loading of poly-(lactic-co-glycolic acid) copolymer-based microparticles containing such medicinal agents as radachlorin (chlorin e6) or ethidium bromide in mesenchymal stem cells was studied. It has been shown that medicinal agents encapsulated inside microparticles affect the loading of these particles in the cytoplasm of mesenchymal stem cells. The number of cells that absorbed the particles with chlorin e6 is approximately two times lower than that in the experiments with ethidium bromide. It has been shown that pretreatment of microparticles with triblock copolymers is more efficient for loading them in cells compared with simultaneous introduction of triblock copolymers and particles into the culture medium. Treatment of ethidium bromide-containing microparticles with triblock copolymers is not efficient for their loading in mesenchymal stem cells compared to the control. The exception is Pluronic 123; when particles are treated with it at concentrations of 1 and 2%, the loading of particles in cells increases compared to the control by factors of approximately 11 and 5, respectively. For particles with chlorin e6, their pretreatment with triblock copolymers at a concentration of 4% is most efficient; the loading of the pretreated particles in cells is increased by factors of approximately 3 to 11. [ABSTRACT FROM AUTHOR]

An innovative type of biodegradable thermoplastic elastomers with improved mechanical properties from very common and potentially renewable sources, poly(L-lactide)-b-poly(2-methyl-1,3-propylene glutarate)-b-poly(L-lactide) (PLA-b-PMPG-b-PLA)s, has been developed for the first time. PLA-b-PMPG-b-PLAs were synthesized by polycondensation of 2-methyl-1,3-propanediol and glutaric acid and successive ring-opening polymerization of L-lactide, where PMPG is an amorphous central block with low glass transition temperature and PLA is hard semicrystalline terminal blocks. The copolymers showed glass transition temperature at lower than −40 °C and melting temperature at 130–152 °C. The tensile tests of these copolymers were also performed to evaluate their mechanical properties. The degradation of the copolymers and PMPG by enzymes proteinase K and lipase PS were investigated. Microbial biodegradation in seawater was also performed at 27 °C. The triblock copolymers and PMPG homopolymer were found to show 9–15% biodegradation within 28 days, representing their relatively high biodegradability in seawater. The macromolecular structure of the triblock copolymers of PLA and PMPG can be controlled to tune their mechanical and biodegradation properties, demonstrating their potential use in various applications.

In this study, we investigated the association of bile salts with pluronic F127 (F127) as a function of their hydrophobicity. Sodium cholate (NaC), sodium deoxycholate (NaDC) and sodium taurodeoxycholate (NaTDC) were used as bile salt. Our interpretations are based on the observations of isothermal titration calorimetry (ITC), high sensitivity differential scanning calorimetry (HSDSC), dynamic light scattering (DLS) and small angle neutron scattering (SANS) experiments. Bile salts affected the aggregation of F127 in accordance to their hydrophobicity, i.e. NaC

In this study, we incorporated carbon nanotubes (CNTs) into poly(styrene-block-isobutylene-block-styrene) (SIBS) to investigate the physical characteristics of the resulting nanocomposite and its cytotoxicity to endothelial cells. CNTs were dispersed in chloroform using sonication following the addition of a SIBS solution at different ratios. The resultant nanocomposite films were analyzed by X-ray microtomography, optical and scanning electron microscopy; tensile strength was examined by uniaxial tension testing; hydrophobicity was evaluated using a sessile drop technique; for cytotoxicity analysis, human umbilical vein endothelial cells were cultured on SIBS–CNTs for 3 days. We observed an uneven distribution of CNTs in the polymer matrix with sporadic bundles of interwoven nanotubes. Increasing the CNT content from 0 wt% to 8 wt% led to an increase in the tensile strength of SIBS films from 4.69 to 16.48 MPa. The engineering normal strain significantly decreased in 1 wt% SIBS–CNT films in comparison with the unmodified samples, whereas a further increase in the CNT content did not significantly affect this parameter. The incorporation of CNT into the SIBS matrix resulted in increased hydrophilicity, whereas no cytotoxicity towards endothelial cells was noted. We suggest that SIBS–CNT may become a promising material for the manufacture of implantable devices, such as cardiovascular patches or cusps of the polymer heart valve.

In this study, a triblock copolymer was used as additive to fabricate new dual layer hollow fiber membranes with a hydrophilic active inner surface in order to improve their fouling resistance. The polymeric components of the solutions for membrane fabrication were poly(ether sulfone), poly(N-vinyl pyrrolidone), and the triblock copolymer. The additive consists of three blocks: a middle hydrophobic poly(ether sulfone) block and two outer hydrophilic alkyl poly(ethylene glycol) blocks. By varying the additive concentration in the solutions, it was possible to fabricate dual layer hollow fiber membranes that are characterized by a hydrophilic inner layer, a pure water permeance of over 1800 L/(m2 bar h) and a molecular weight cut-off of 100 kDa similar to commercial membranes. Contact angle and composition determination by XPS measurements revealed the hydrophilic character of the membranes, which improved with increasing additive concentration. Rheological, dynamic light scattering, transmission, and cloud point experiments elucidated the molecular interaction, precipitation, and spinning behavior of the solutions. The low-molecular weight additive reduces the solution viscosity and thus the average relaxation time. On the contrary, slow processes appear with increasing additive concentration in the scattering data. Furthermore, phase separation occurred at a lower non-solvent concentration and the precipitation time increased with increasing additive content. These effects revealed a coupling mechanism of the triblock copolymer with poly(N-vinyl pyrrolidone) in solution. The chosen process parameters as well as the additive solutions provide an easy and inexpensive way to create an antifouling protection layer in situ with established recipes of poly(ether sulfone) hollow fiber membranes. Therefore, the membranes are promising candidates for fast integration in the membrane industry.

The purpose of this study was to investigate the effects of size and type of incorporated model molecules on the polymer degradation and release profile from thermosensitive triblock copolymer based controlled delivery systems. In vitro release of the incorporated molecules demonstrated slow release for risperidone (molecular weight (Mw) = 410.48 Da; partition coefficient (Ko/w) = 3.49), while bovine serum albumin (BSA) (Mw = ~66,400 Da; Ko/w = 0.007) and insulin (Mw = 5808 Da; Ko/w = 0.02) showed initial burst release followed by controlled release. The proton NMR, Gel Permeation Chromatography, and Cryo-SEM studies suggest that the size and partition coefficient of incorporated molecules influence the pore size, polymer degradation, and their release. In spite of using a similar polymer delivery system the polymer degradation rate and drug release notably differ for these model molecules. Therefore, size and oil-water partition coefficient are important factors for designing the controlled release formulation of therapeutics from triblock copolymer based delivery systems.

Gastric cancer, a high-risk malignancy, is a genetic disease developing from a cooperation of multiple gene mutations and a multistep process. Gene therapy is a novel treatment method for treating gastric cancer. Here, we developed a novel Arg-Gly-Asp (RGD) peptides conjugated copolymers nanoparticles-based gene delivery system in order to actively targeting inhibit the growth of gastric cancer cells. These transcription factor (AP-2α) expression plasmids were also encapsulated into pluronic triblock copolymers nanoparticles which was constituted of poly(ethylene glycol)-block-poly(propylene glycol)- block-poly(ethylene glycol) (PEO-block-PPO-block-PEO, P123). The size, morphology and composition of prepared nanocomposites were further characterized by nuclear magnetic resonance (NMR), transmission electron microscopy (TEM) and dynamic light scattering (DLS). In MTT (3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide) analysis, these nanocomposites have minor effects on the proliferation of GES-1 cells but significantly decreased the viability of MGC-803, suggesting they own low cytotoxicity but good antitumor activity. The following in vivo evaluation experiments confirmed that these nanocomposites could prevent the growth of gastric cancer cells in the tumor xenograft mice model. In conclusion, these unique RGD peptides conjugated P123 encapsulated AP-2α nanocomposites could selectively and continually kill gastric cancer cells by over-expression of AP-2α in vitro and in vivo; this exhibits huge promising applications in clinical gastric cancer therapy.

A series of tertiary amine containing PHMEMA-PEG-PHMEMA ABA triblock copolymers were synthesized by atom transfer radical polymerization (ATRP) using bromine-capped poly(ethylene glycol) (Br-PEG-Br) and 2-(hexamethyleneimino)ethyl methacrylate (HMEMA) as macro-initiator and monomers, respectively. The chemical structures and molecular weights of triblock copolymers were characterized by 1H NMR and gel permeation chromatography (GPC). The self-assembly behaviors of copolymers in different pH conditions were studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM). Triblock copolymers self-assembled into micelles in water (pH 7.4) and the micelles disassembled at acidic pH (pH 5.0). Anticancer drug doxorubicin (DOX) was used as a drug model and physically encapsulated into polymeric micelles. The drug release of DOX-loaded polymeric micelles was pH-responsive; the drug-loaded micelles that had higher contents of tertiary amine in polymer pendant groups showed faster release speed. In addition, the drug-loaded micelles showed excellent inhibition efficacy against HeLa cells in vitro. [ABSTRACT FROM AUTHOR]

Controlled degradation of polymers and tandem living polymerization methodology offer astonishing opportunities to recombine different kinds of polymers and monomers into valuable, well-defined copolymers with excellent properties and wide application prospects. In this work, the possibility of synthesizing ABA triblock copolymers by combining cross metathetic degradation of poly-butadiene (PB) with ring-opening polymerization of d , l -lactide was studied and confirmed. The effects of the reaction time and the concentration of the chain transfer agent (CTA) on the final molecular weights of the telechelic polymers were investigated. As a result, a new and high valuable α,ω-diol-ended PB (macro-CTA) was synthesized by the metathetic degradation of PB with acyclic olefin ( cis -1,4-diacetoxy-2-butene) as the CTA, which was then hydrolyzed. With Sn(Oct) 2 as the catalyst, the reaction of difunctional macro-CTA with d , l -lactide was successfully realized and series of well-defined ABA triblock copolymers with different molecular weights were achieved. [ABSTRACT FROM AUTHOR]

Poly(ϵ-caprolactone)-b-poly(ethylene glycol)-b-poly(ϵ-caprolactone) (PCL-b-PEG-b-PCL) triblock copolymer were synthesized by mean anionic activation of the hydroxyl end groups of poly(ethylene glycol) in presence of diphenylmethylsodium. Copolymers were characterized by SEC, FT-IR and 1H-NMR spectroscopy, TGA and DSC. Size exclusion chromatographic analysis of obtained copolymers indicated incorporation of CL monomer into PEG without formation of PCL homopolymer. Characterization by FT-IR and 1H NMR spectroscopy of the resulting polymeric products, with respect to their structure, end-groups and composition, showed that they are best described as ester-ether-ester triblock copolymers, whose compositions can be adjusted changing the feeding molar ratio of PEG to CL. The thermal stability of triblock copolymers was less that PEG precursor, but higher that PCL homopolymer. Analysis by mean DSC showed that all copolymers were semi-crystalline and their thermal behavior depending on their composition. [ABSTRACT FROM AUTHOR]

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (Mn 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by 1H NMR, quantitative 13C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (< 2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers. [ABSTRACT FROM AUTHOR]

Abstract: High‐performance n‐type thermoelectric polymers are vital in the development of polymer thermoelectric generators (PTEGs). However, the progress is very slow due to their low stability and low thermoelectric properties. Here, aniline oligomer‐block‐polyethylene glycol‐block‐aniline oligomer (ANI)n‐b‐PEO‐b‐(ANI)n) (n = 4, 8, 16) are prepared and studied. The results indicate that the (ANI)n‐b‐PEO‐b‐(ANI)n show unique temperature sensitivity and switch from p‐type to n‐type when the temperature is above 300 K. Differential scanning calorimetry curves show that the Tg of the (ANI)n‐b‐PEO‐b‐(ANI)n is lower than 300 K, indicating that PEO segments of the (ANI)n‐b‐PEO‐b‐(ANI)n easily move above 300 K and have high flexibility. Temperature‐dependent Raman spectra confirm that there are strong interactions between PEO segments and aniline oligomers during the raising temperature, and PEO chains might provide plenty of negative charge at high temperature, which can convert the (ANI)n‐b‐PEO‐b‐(ANI)n into n‐type thermoelectric materials. To adjust the number of aniline unit, (ANI)8‐b‐PEO‐b‐(ANI)8 shows excellent n‐type characteristics with Seebeck coefficient as large as −1171 µV K−1 at 381 K. The strong interaction between PEO and aniline oligomers plays a dominant role in the n‐type thermoelectric performance of the triblock copolymers, which have potential application in the field of PTEGs and temperature sensors. [ABSTRACT FROM AUTHOR]

Nonionic surfactants, triblock copolymers (TBCs), were used to obtain and stabilize perfluorocarbon emulsions in a water solution (drop size, 200-300 nm). These TBCs differ in their molecular weight, length of polyethylene glycol (PEG) or polypropylene glycol (PPG) chains, and the ΣPEG/ΣPPG parameter value. Direct dependence is found between the amount of plasma proteins adsorbed on drops and the PEG/PPG value. The amount of the adsorbed proteins and their total mass per unit surface of the drop decreases as this ratio is reduced. Meanwhile, protein adsorption is almost independent of the molecular weight of TBCs and the length of PEG and PPG blocks. Adsorption of non-protein substance, chlorine e6, on emulsion drops increases with the rising ΣPEG/ΣPPG value and does not depend on other characteristics of TBC used as a stabilizer. [ABSTRACT FROM AUTHOR]