Resulting Block Copolymers Research Articles

Preparation of Degradable Polymeric Nanoparticles with Various Sizes and Surface Charges from Polycarbonate Block Copolymers

ABA-type polycarbonate block copolymers with pendant vinyl ether and benzyl functionalities were synthesized by sequential ring-opening polymerization of functional cyclic carbonate monomers using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an organobase catalyst. The vinyl ether moieties on the resulting block copolymers were readily conjugated with 3-mercaptopropionic acid, cysteamine hydrochloride, and L-cysteine hydrochloride monohydrate through thiol-ene “click” reactions, yielding anionic, cationic, and zwitterionic self-assembled nanoparticles, respectively, in corresponding buffers. The effect of pH on the size and surface charge of nanoparticles were examined.

Hierarchically Porous Copolymer Film as Immobilization Matrix for Phenol Biosensor with High Sensitivity

A hierarchically porous structure of the matrix for immobilization of bioactive molecules is of crucial importance in improving the performance of electrochemical biosensors. In the present work, a block copolymer film was prepared via spinodal-decomposition-induced macro- and mesophase separation plus extraction by rinsing (SIM2PLE). The film exhibited an interconnected porous structure including macropores and mesopores. Thus, the specific surface area of the film was greatly enhanced, which was a benefit to the subsequent immobilization of enzyme. Then the resultant porous block copolymer film was adopted to construct a high-performance electrochemical biosensor to detect phenolic compounds. The as-developed phenolic biosensor exhibited a high sensitivity (3.0 × 103 mA·M–1·cm–2), quick response (<5 s), and extremely low detection limit (7 nM at an S/N ratio of 3). Moreover,a decent linear range (0.02–35 μM) was also observed. This work demonstrates that the hierarchically porous film based on copolymer...

Highly Fluorescent Benzophosphole Oxide Block-Copolymer Micelles

The efficient synthesis of highly fluorescent para-biphenyl-substituted benzophospholes via zirconium-mediated metallacycle transfer is reported. A norbornene-appended benzophosphole oxide monomer was found to readily undergo living ring-opening metathesis polymerization with the Grubbs third-generation catalyst to yield either a homopolymer or block copolymers. The resulting block copolymers consisting of lipophilic alkylated- or pinacolboronate-capped comonomers undergo self-assembly into spherical micelles in tetrahydrofuran/hexanes mixtures, as determined by dynamic light scattering and transmission electron microscopy. One hallmark of the benzophosphole-containing polymers is their greatly enhanced emission intensity in solution in relation to their monomers, presumably due to a restriction in molecular motion upon formation of homopolymers or assembled block-copolymer micelles. Evidence for “analyte amplified precipitation” was found, wherein addition of a substoichiometric amount of fluoride to a b...

1,4-Regulated Thermoplastic Elastomers

A series of 3-methylenecyclopentene (MCP) based block polymers are prepared by sequential polymerization of MCP, isoprene (IP) and/or butadiene (BD) by using rare-earth metal cationic catalyst. The resulting block copolymers are constituted by 1,4-poly(MCP), cis- 1,4-poly(IP) and cis-1,4-poly(BD), which afforded AB type, ABA-type and ABC type copolymers. The AFM micrographs of triblock copolymer showed a remarkable phase-separation morphology of the 1,4-poly(MCP) block and cis-1,4-poly(IP).

Dielectric spectroscopy of novel bio-based aliphatic-aromatic block copolymers: Poly(butylene terephthalate)-b-poly(lactic acid).

Broadband dielectric spectroscopy has been used to characterize in deep the relaxation behavior of novel bio-based aliphatic-aromatic block copolymers based on poly(butylene terephthalate) (PBT) and poly(lactic acid) (PLA). The results indicate that the copolymerization decreases the ability to crystallize of the resulting block copolymer. The [Formula: see text] relaxation of the block copolymers is consistent with this fact exhibiting initially the characteristics features of an amorphous polymeric material cold crystallizing upon heating. The cold crystallization can be easily visualized by dielectric spectroscopy by a discontinuous and abrupt change of the shape parameters of the [Formula: see text] relaxation. The sub-glass dynamics of the block copolymers is complex and be ascribed to a [Formula: see text] relaxation composed of two local modes, [Formula: see text] and [Formula: see text], which can be assigned to the relaxation in PBT of the bond between the ester oxygen and the aliphatic carbon and to the bond between the aromatic ring carbon to the ester carbon, respectively. With increasing amount of the PLA block the crystallinity decreases as well as the activation energy of the [Formula: see text] mode approaching the expected value for amorphous PBT. On the contrary, the activation energy for the [Formula: see text] exhibits an unexpected increase as the amount of PLA increases. This effect has been explained by considering that at lower temperatures the [Formula: see text] mode of PBT is the more significant while at higher temperatures the [Formula: see text] relaxation of the PLA block becomes the dominant one.

Synthesis of polypeptide bearing 1,4-dithiane pendants for ROS-responsive drug release

Stimuli-responsive polypeptides have been intensively investigated for controlled drug release, owing to their favorable biocompatibility and biodegradability. In this work, we designed and synthesized a new kind of polypeptide bearing 1,4-dithiane pendants for reactive oxygen species (ROS)-responsive drug release. The polypeptide-based block copolymer was facilely synthesized by ring-opening polymerization (ROP) of 1,4-dithian-substituted l-glutamate N-carboxyanhydride (DTG-NCA) monomer using an amino-terminated poly(ethylene glycol) methyl ether (mPEG-NH2) as the macromolecular initiator. The resultant block copolymer, mPEG-b-PDTG, could self-assemble into uniform micelles in aqueous medium owing to its amphiphilic structure. Then, the H2O2-triggered oxidation behaviors of the mPEG-b-PDTG micelles were studied by dynamic light scattering (DLS), FT-IR and turbidimetric assay. It was revealed that the oxidation of thioether into sulfoxide in the side chains would result in disassembly of the micelles. Furthermore, the ROS-responsive drug release behavior of the mPEG-b-PDTG micelles was verified by using Nile Red as a model drug. MTT assay also proved that mPEG-b-PDTG was non-toxic in B16F10 and L929 cells. Therefore, such a new class of oxidation-responsive polypeptide might provide a promising platform for ROS-responsive drug delivery.

Light-responsive block copolymers with a spiropyran located at the block junction

Block copolymers with a functional group between their blocks are relatively little explored even though this molecular architecture can reduce the aggregation of the functional groups, promote the phase separation in nanophase-separated materials, and has other interesting effects. Spiropyrans are well-known for their ability to switch to their polar merocyanine form in response to light, force and other stimuli. The synthesis of stimuli-responsive AB-type block copolymers with spiropyran moieties located at the junction of the blocks is presented here. A homopolymer is synthesized from a trimethylindolenine-based atom transfer radical polymerization (ATRP) initiator, followed by its modification to a spiropyran end-functionalized polymer. The spiropyran functionalized polymer is then used as a macro-initiator for the synthesis of a second polymer block by ring opening polymerization (ROP). Alternatively, spiropyran homopolymers are conjugated to other preformed polymers by esterification. The resulting block copolymers reversibly switch under UV and white light irradiation over multiple cycles, and a block copolymer reduced the tendency of the merocyanine to aggregate during switching. The stimuli-responsive block copolymer could be useful for a range of applications, e.g. for bioinspired polymersome nanoreactors, or in membranes with switchable permeability.

The effect of cationic groups on the stability of 19F MRI contrast agents in nanoparticles

ABSTRACTFluorine‐19 (19F)‐based contrast agents are increasingly used for magnetic resonance imaging. Conjugated to polymers, they provide an excellent quantitative imaging tool to detect the movement of the polymeric nanoparticles in vivo as there is no background signal in tissue. One of the challenges is the decline in signal intensity when the conjugated hydrophobic fluorinated functionalities aggregate. Therefore, a new fluorinated monomer was prepared from l‐arginine that carries a 2,2,2‐trifluoroethyl functional group for imaging. The resulting monomer, 2,2,2‐trifluoroethylamide l‐arginine methacrylamide (3FArgMA), was copolymerized with poly(ethylene glycol) methyl ether methacrylate (PEGMEMA), [2‐(2,3,4,6‐tetra‐O‐acetyl‐α‐d‐mannopyranosyloxy)ethyl methacrylate or 1‐O‐methacryloyl‐2,3:4,5‐di‐O‐isopropylidene‐β‐d‐fructopyranose, respectively, using poly(methyl methacrylate) macro‐reversible addition–fragmentation chain transfer polymerization agent. The resulting block copolymers, which varied in 3FArgMA content, were self‐assembled into micelles of hydrodynamic diameters from 25 to 60 nm. The permanently positively charged arginine functionality on the 3FArgMA displayed repulsive forces against aggregation enabling high spin–spin relaxation times (T2) in acidic as well as alkaline solutions. However, the longer poly(ethylene glycol) side functionality in PEGMEMA enabled better steric stabilization (T2~30 ms) while the short fructose side chain was not enough to maintain high T2 values, in particular when a higher 3FArgMA content was used. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1994–2001

Polymeric Micelles Based on Light-Responsive Block Copolymers for the Phototunable Detection of Mercury(II) Ions Modulated by Morphological Changes.

Polymeric micelles based on light-responsive block copolymers were prepared and used for the phototunable detection of mercury(II) ions. 2-Nitrobenzyl acrylate (NBA) and ( E)-2-((4-((4-formylphenyl)diazenyl)phenyl)(methyl)amino) ethyl acrylate (FPDEA) were copolymerized from a poly(ethylene oxide) (PEO) macroinitiator via atom transfer radical polymerization (ATRP), leading to a well-defined block copolymer of PEO113- b-[p(NBA10- co-FPDEA3)] with a low polydispersity index (PDI = 1.16). After polymerization, the aldehyde groups of PEO- b-[p(NBA- co-FPDEA)] were converted to aldoxime groups by reacting with hydroxylamine, leading to the formation of a final oxime-containing polymeric probe, PEO- b-[p(NBA- co-HPDEA)], P1. The resulting block copolymer, P1, was self-assembled in water to yield spherical micelles that consist of a PEO block forming a hydrophilic shell and a copolymer of light-responsive NBA and a mercury(II) ion-detecting HPDEA block forming a hydrophobic core. Upon the addition of mercury(II) ions to this micellar solution, no detection was observed since water-soluble mercury(II) ions have limited accessability to the oxime units of P1, which are located in the hydrophobic core. After UV light irradiation, however, the photolabile 2-nitrobenzyl moieties were cleaved, and hydrophobic PNBA was transformed to hydrophilic poly(acrylic acid) (PAA), leading to the photoinduced dissociation of micelles to unimers. As a result, the oxime units of P1 were exposed to a hydrophilic environment and could react with mercury(II) ions to form nitrile groups, resulting in the turn-on detection of mercury(II) ions by UV light irradiation.

Use of Sulfobetaine-Based Block Copolymer as Stabilizer in Silver Nanoparticle Production and Catalytic Activity Studies.

A zwitterionic sulfobetaine-based diblock copolymer was successfully synthesized and used in the preparation and stabilization of Ag nanoparticles (AgNPs). For the related block copolymer, a precursor AB type diblock copolymer was synthesized via atom transfer radical polymerization by using a MPEG-based ATRP macroinitiator and 2-(N-dimethylamino)ethyl methacrylate (DMA) comonomer. Tertiary amine residues of PDMA blocks in poly(ethylene glycol) methyl ether-b-poly[2-(N-diethylamino)ethyl methacrylate] (MPEG-b-PDMA) precursor was then converted to polybetaine structures by reacting with 1,3-propanesultone to obtain poly(ethylene glycol) methyl ether-b-poly[3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate] (MPEG-b-PβDMA) derivative. The resulting block copolymer was successfully used as stabilizer in the chemical and sonochemical synthesis of spherical AgNPs with a diameter in the range of 7.9-9.3 nm. The average diameter of AgNPs synthesized by sonochemical method was smaller than those synthesized by chemical method. The MPEG-b-PβDMA diblock copolymer was determined to be a good stabilizer for AgNPs. The AgNPs dispersion was stable for more than 5 months without any flocculation at room temperature. The catalytic activity of polymer-AgNP dispersion was also investigated in the reduction of p-nitrophenol to p-aminophenol and was found to be quite effective.

수산기 말단 폴리부타디엔을 개시제로 사용한 에피클로로히드린의 양이온 개환 중합과 그 결과물의 아지드화 반응

수산기 말단 폴리부타디엔을 개시제로 사용한 에피클로로히드린의 양이온 개환 중합과 그 결과물의 아지드화 반응

A One‐Step Route to CO2‐Based Block Copolymers by Simultaneous ROCOP of CO2/Epoxides and RAFT Polymerization of Vinyl Monomers

AbstractThe one‐step synthesis of well‐defined CO2‐based diblock copolymers was achieved by simultaneous ring‐opening copolymerization (ROCOP) of CO2/epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC‐COOH) as the bifunctional chain transfer agent (CTA). The double chain‐transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09–1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC‐COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO2‐based polycarbonates.

A One‐Step Route to CO2‐Based Block Copolymers by Simultaneous ROCOP of CO2/Epoxides and RAFT Polymerization of Vinyl Monomers

The one-step synthesis of well-defined CO2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO2 -based polycarbonates.

Synthesis of CO2-Based Block Copolymers via Chain Transfer Polymerization Using Macroinitiators: Activity, Blocking Efficiency, and Nanostructure

Immortal copolymerization of epoxides/CO2 using macro-chain-transfer agent (macro-CTA) is a useful method to prepare CO2-based block copolymers for manufacturing high value-added materials. Despite a variety of CO2-based block copolymers that have been reported using distinct macro-CTAs, issues including catalytic activity and blocking efficiency for the immortal polymerization remain superficially understood. Here, we systematically studied the reaction activity and blocking efficiency by using various macro-CTAs (including PPG, PEG, and PS) in the presence of two classical catalyst systems ((BDI)ZnOAc and SalenCoTFA/PPN-TFA). By analysis of the gel permeation chromatograms via mathematical deconvolution, it comes to a conclusion that the size, nature, and ratio of [macro-CTA]/[Cat.] strongly influence the catalytic activity of the reaction and blocking efficiency for the resultant block copolymers. Thin film self-assembly of PS/PPC block copolymers was investigated, and the results were analyzed by SEM ...

Highly Efficient One-Pot Synthesis of COS-Based Block Copolymers by Using Organic Lewis Pairs.

A one-pot synthesis of block copolymer with regioregular poly(monothiocarbonate) block is described via metal-free catalysis. Lewis bases such as guanidine, quaternary onium salts, and Lewis acid triethyl borane (TEB) were equivalently combined and used as the catalysts. By using polyethylene glycol (PEG) as the macromolecular chain transfer agent (CTA), narrow polydispersity block copolymers were obtained from the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO). The block copolymers had a poly(monothiocarbonate) block with perfect alternating degree and regioregularity. Unexpectedly, the addition of CTA to COS/PO copolymerization system could dramatically improve the turnover frequency (TOF) of PO (up to 240 h−1), higher than that of the copolymerization without CTA. In addition, the conversion of CTA could be up to 100% in most cases, as revealed by 1H NMR spectra. Of consequence, the number-average molecular weights (Mns) of the resultant block copolymers could be regulated by varying the feed ratio of CTA to PO. Oxygen-sulfur exchange reaction (O/S ER), which can generate randomly distributed thiocarbonate and carbonate units, was effectively suppressed in all of the cases in the presence of CTA, even at 80 °C. This work presents a versatile method for synthesizing sulfur-containing block copolymers through a metal-free route, providing an array of new block copolymers.

Spontaneous Hydrogel Formation Through Hydrophobic Interactions in an ABA-type Block Copolymer Composed of Poly(2-methacryloyloxyethyl phosphorylcholine) and Poly(n-butyl methacrylate) Segments

ABSTRACTIn this study, the spontaneous formation of hydrogels from a water-soluble and amphiphilic ABA-type block copolymer in an aqueous system was examined. The block copolymers were composed of poly(2-methacryloyloxyethyl phosphorylcholine) (MPC) as the B segment and poly(n-butyl methacrylate) (BMA) as the A segment. A two-step living radical polymerization of the corresponding monomers yielded a well-defined ABA-type block copolymer. By regulating the polymerization degree of each segment, the water solubility and amphiphilic natures of the resulting block copolymer could be controlled. The block copolymers spontaneously formed hydrogels when the composition of water in the medium increased to 80 vol% in the water/ethanol mixture. This was due to molecular aggregation of the block copolymers driven by the hydrophobic interactions between the poly(BMA) segments in the polymer. This hydrogel formation depended on the composition and polymerization degree of the MPC units. The poly(MPC) also showed good biocompatibility, thereby rendering the block copolymers applicable for the immobilization of biological components such as antibodies and enzymes and the encapsulation of cells under mild conditions.

RAFT synthesis of polystyrene‐block‐poly(polyethylene glycol monomethyl ether acrylate) for zinc phthalocyanine‐loaded polymeric micelles as photodynamic therapy photosensitizers

ABSTRACTA series of polystyrene‐block‐poly(polyethylene glycol monomethyl ether acrylate) (PStm‐b‐PPEGAn) polymers were systematically synthesized as carriers for zinc phthalocyanine (ZnPc) for photodynamic therapy via reversible addition and fragmentation chain transfer polymerization. The degree of polymerization of the styrene (m) and PEGA units (n) of the resulting block copolymers were characterized to be n = 174, 40, and 18 for m = 52; and n = 200, 84, and 31 for m = 30. All the block copolymers formed micelles in water. The critical micelle concentration (CMC) of the PStm‐b‐PPEGAn was determined by fluorometry using pyrene as a hydrophobic probe. The CMC value increased from 4.5 to 20 mg·L−1 with an increase in the mole fraction of PEGA units. The median diameters of the micelles increased from 19 to 31 nm for PSt52‐b‐PPEGAn and from 15 to 23 nm for PSt30‐b‐PPEGAn with increasing n value. ZnPc‐loaded micelles were prepared by dialysis of the block copolymer in the presence of ZnPc followed by removal of large aggregates by filtration. The encapsulation efficiency was dramatically changed in the range of 0–68%. The light‐dose‐dependent cytotoxicity of the ZnPc‐loaded PSt30‐b‐PPEGA200 was clearly established in HeLa cell lines; while no cytotoxicity was confirmed under the dark. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 560–570

Synthesis of Polysulfone-Containing Poly(butylene terephthalate) Segmented Block Copolymers: Influence of Segment Length on Thermomechanical Performance

A facile synthesis of hydroxyethyl-functionalized poly(ether sulfone) (PESu) oligomers permitted subsequent melt transesterification into segmented block copolymers with poly(butylene terephthalate). The unique solubility of the PESu oligomers in the melt with 1,4-butanediol and dimethyl terephthalate enabled a systematic study of segment length on thermomechanical properties of the resulting block copolymers. 1H NMR spectroscopy revealed a compositional dependence on the average segment length of the PBT. Additionally, the concert of NMR spectroscopy, DSC, and DMA highlighted critical segment lengths for crystallization and phase separation. In agreement with a relatively constant Tm and phase separation observed with DSC and DMA, respectively, small-angle X-ray scattering identified a compositionally independent lamellar thickness, while the amorphous layer thickness increased with PESu incorporation. As a result, the complementary analytical techniques provided an understanding of the morphological inf...

Incorporation of benzothiadiazole moiety at junction of polyfluorene–polytriarylamime block copolymer for effective color tuning in organic light emitting diode

ABSTRACTBlock copolymer consisting of polyfluorene and polytriarylamine with benzothiadiazole moiety at the junction is prepared in order to obtain an orange emitting polymer via Suzuki‐Miyaura followed by Buchwald‐Hartwig coupling reactions. Electroluminescent device fabricated with resulting block copolymer exhibit only orange emission, although slight blue emission is observed in the fluorescent spectrum for the thin film, indicating that benzothiadiazole part plays a role of an effective trap site. Devices based on polyfluorene homopolymer doped with block copolymer (10 wt %) or an orange emitting model compound at the corresponding content of benzotiadiazole unit are also fabricated. The device with the model compound exhibits orange emission with Commission Internationale de l'Éclairage (CIE) coordinate of (0.58, 0.42), whereas that with block copolymer pale orange with the coordinate of (0.44, 0.38). This fact is probably due to the preferential distribution of block copolymer at the vicinity of anode via hydrophilic interaction of trioxyethylene side chains with poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45393.

PH-Induced reversible formation of core-crosslinked star polymers

Core-crosslinked star (CCS) polymers with polyethylene oxide (PEO) as a shell and crosslinked poly(4-vinylbenzylamine) (PVBA) derivatives as a core, were successfully synthesized by ‘arm-first’ method. Tert-butyloxycarbonyl (t-boc)-protected VBA (tVBA), potentially containing primary amine, was polymerized from a PEO macroinitiator by atom transfer radical polymerization to yield PEO-b-PtVBA block copolymer. The t-boc protecting groups of the resulting block copolymer were deprotected via trifluoroacetic acid (TFA) to generate PEO-b-PVBA with the primary amine functionality. The primary amine groups of PEO-b-PVBA were self-coupled in the presence of vanadium oxide (V2O5) and hydrogen peroxide via imine bond formation, leading to the CCS polymers. Dynamic light scattering results of CCS polymers showed that the hydrodynamic diameter of CCS polymers was larger than that of the initial PEO-b-PVBA block copolymer, demonstrating the successful formation of CCS polymers. Well-dispersed individual globular CCS polymers were visualized by atomic force microscopy. The imine linkages of CCS polymers were hydrolyzed at pH 4, yielding individual polymer chains. The CCS polymers were reversibly formed again above pH 8.