Water-soluble Block Copolymers Research Articles

The Coordination of Aluminum Sulfate with a Water-Soluble Block Copolymer Containing Carboxyl, Amide, Sulfonic and Anhydride Groups Providing Both Accelerating and Hardening Effects in Cement Setting

Two water-soluble block copolymers composed of acrylic acid (AA), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), and optionally maleic anhydride (MAH) were synthesized through ammonium persulfate-catalyzed free radical polymerization in water. The introduction of aluminum sulfate (AS) into the resulting mixtures significantly reduced the setting times of the paste and enhanced the mechanical strength of the mortar compared to both the additive-free control and experiments facilitated solely by pure AS. This improvement was primarily attributed to the inhibition of rapid Al3+ hydrolysis, which was achieved through coordination of the synthesized block copolymers, along with the formation of newly identified hydrolytic intermediates. Notably, the ternary copolymer (AA–AMPS–MAH) exhibited superior performance compared to that of the binary copolymer (AA–AMPS). In the early stages of cement setting, clusters of ettringite (AFt) were found to be immobilized over newly detected linkage phases, including unusual calcium silicate hydrate and epistilbite. In contrast to the well-documented role of polymers in retarding cement hydration, this study presents a novel approach by providing both accelerating and hardening agents for cement setting, which has significant implications for the future design of cement additives.

Architecting Multicompartmentalized, Giant Vesicles with Recombinant Fusion Proteins.

We present a straightforward strategy for constructing giant, multicompartmentalized vesicles using recombinant fusion proteins. Our method leverages the self-assembly of globule-zipper-elastin-like polypeptide fusion protein complexes in aqueous conditions, eliminating the need for organic solvents and chemical conjugation. By employing the thin-film rehydration method, we have successfully encapsulated a diverse range of bioactive macromolecules and engineered organelle-like compartments─ranging from soluble proteins and coacervate droplets to vesicles─within these protein-assembled giant vesicles. This approach also facilitates the integration of water-soluble block copolymers, enhancing the structural stability and functional versatility of the vesicles. Our results suggest that these multicompartment giant protein vesicles not only mimic the complex architecture of living cells but also support biochemically distinct reactions regulated by functionally folded proteins, providing a robust model for studying cellular processes and designing microreactor systems. This work highlights the transformative potential of self-assembling recombinant fusion proteins in artificial cell design.

Photocleavable Visible Light-Triggered Anthraquinone-Derived Water-Soluble Block Copolymer for Peroxynitrite Generation in Cancer Therapy.

We report a facile stimuli-responsive strategy to generate reactive oxygen and nitrogen species (ROS and RNS) in the biological milieu from a photocleavable water-soluble block copolymer under visible light irradiation (427 nm, 2.25 mW/cm2). An anthraquinone-based water-soluble polymeric nitric oxide (NO) donor (BCPx-NO) is synthesized, which exhibits NO release in the range of 40-65 μM within 10 h of photoirradiation with a half-life of 30-103 min. Additionally, BCPx-NO produces peroxynitrite (ONOO-) and singlet oxygen (1O2) under photoirradiation. To understand the mechanism of NO release and photolysis of the functional group under blue light, we prepared a small-molecule anthraquinone-based N-nitrosamine (NOD). The cellular investigation of the effect of spatiotemporally controlled ONOO- and 1O2 generation from the NO donor polymeric nanoparticles in a triple negative breast adenocarcinoma (MDA-MB-231) under visible light irradiation (white light, 5.83 mW/cm2; total dose 31.5 J/cm2) showed an IC50 of 0.6 mg/mL. The stimuli-responsive strategy using a photolabile water-soluble block copolymer employed to generate ROS and RNS in a biological setting widens the horizon for their potential in cancer therapy.

A chemically engineered water-soluble block copolymer for redox responsive SO2 release in antibacterial therapy.

Sulfur dioxide (SO2) has emerged as a promising gasotransmitter for various therapeutic applications, including antibacterial activities. However, the potential of polymeric SO2 donors for antimicrobial activities remains largely unexplored. Herein, we report a water-soluble, redox-responsive, SO2-releasing amphiphilic block copolymer poly(polyethylene glycol methyl ether methacrylate) (PPEGMA)-b-poly(2-((2,4-dinitrophenyl)sulfonamido)ethyl methacrylate (PM)) (BCPx) to investigate their antibacterial properties. BCPx contains hydrophilic polyethylene glycol (PEG) pendants and a hydrophobic SO2-releasing PM block, facilitating the formation of self-assembled nanoparticles (BCPxNp) in an aqueous medium, studied by critical aggregation concentration (CAC) measurements, dynamic light scattering (DLS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). BCPxNp exhibits sustained SO2 release up to 12 h in the presence of glutathione (GSH), with a yield of 30-80% of theoretical SO2 release. In vitro antibacterial studies unveil the outstanding antibacterial activity of BCP3Np against Gram-positive bacteria Bacillus subtilis, as evidenced by FESEM and live/dead cell fluorescence assay. We further elucidate the antibacterial mechanism through reactive oxygen species (ROS) generation studies. Overall, the polymer exhibits excellent biocompatibility at effective antimicrobial concentrations and provides insights into the design of a new class of SO2-releasing polymeric antibacterial agents.

Photostimulated Extended Nitric Oxide (NO) Release from Water-Soluble Block Copolymer to Enhance Antibacterial Activity.

N-Nitrosamines are well established motifs to release nitric oxide (NO) under photoirradiation. Herein, a series of amphiphilic N-nitrosamine-based block copolymers (BCPx-NO) are developed to attain controlled NO release under photoirradiation (365 nm, 3.71 mW/cm2). The water-soluble BCPx-NO forms micellar architecture in aqueous medium and exhibits a sustained NO release of 92-160 μM within 11.5 h, which is 36.8-64.0% of the calculated value. To understand the NO release mechanism, a small molecular NO donor (NOD) resembling the NO releasing functional motif of BCPx-NO is synthesized, which displays a burst NO release in DMSO within 2.5 h. The radical nature of the released NO is confirmed by electron paramagnetic resonance (EPR) spectroscopy. The gradual NO release from micellar BCPx-NO enhances antibacterial activity over NOD and exhibits a superior bactericidal effect on Gram-positive Staphylococcus aureus. In relation to biomedical applications, this work offers a comprehensive insight into tuning light-triggered NO release to improve antibacterial activity.

Poly(Oxanorbornene)-Protein Conjugates Prepared by Grafting-to ROMP as Alternatives for PEG.

PEGylation is the gold standard in protein-polymer conjugation, improving circulation half-life of biologics while mitigating the immune response to a foreign substance. However, preexisting anti-PEG antibodies in healthy humans are becoming increasingly prevalent and elicitation of anti-PEG antibodies when patients are administered with PEGylated therapeutics challenges their safety profile. In the current study, two distinct amine-reactive poly(oxanorbornene) (PONB) imide-based water-soluble block co-polymers are synthesized using ring-opening metathesis polymerization (ROMP). The synthesized block-copolymers include PEG-based PONB-PEG and sulfobetaine-based PONB-Zwit. The polymers are then covalently conjugated to amine residues of lysozyme (Lyz) and urate oxidase (UO) using a grafting-to bioconjugation technique. Both Lyz-PONB and UO-PONB conjugates retained significant bioactivities after bioconjugation. Immune recognition studies of UO-PONB conjugates indicated a comparable lowering of protein immunogenicity when compared to PEGylated UO. PEG-specific immune recognition is negligible for UO-PONB-Zwit conjugates, as expected. These polymers provide a new alternative for PEG-based systems that retain high levels of activity for the biologic while showing improved immune recognition profiles.

Two-Dimensional Supramolecular Polymerization of DNA Amphiphiles is Driven by Sequence-Dependent DNA-Chromophore Interactions.

Two-dimensional (2D) assemblies of water-soluble block copolymers have been limited by a dearth of systematic studies that relate polymer structure to pathway mechanism and supramolecular morphology. Here, we employ sequence-defined triblock DNA amphiphiles for the supramolecular polymerization of free-standing DNA nanosheets in water. Our systematic modulation of amphiphile sequence shows the alkyl chain core forming a cell membrane-like structure and the distal π-stacking chromophore block folding back to interact with the hydrophilic DNA block on the nanosheet surface. This interaction is crucial to sheet formation, marked by a chiral "signature", and sensitive to DNA sequence, where nanosheets form with a mixed sequence, but not with a homogeneous poly(thymine) sequence. This work opens the possibility of forming well-ordered, bilayer-like assemblies using a single DNA amphiphile for applications in cell sensing, nucleic acid therapeutic delivery and enzyme arrays.

Well-Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water-Soluble Stereoregular Telechelic Poly(phenylacetylene)s.

Well-controlled living polymerization of water-soluble phenylacetylene derivatives in water was achieved for the first time using a multicomponent catalytic system consisting of [Rh(nbd)Cl]2 , an aryl boronic acid, diphenylacetylene having carboxy groups, a tetraalkylammonium hydroxide, and a water-soluble triphenylphosphine. This catalytic system enables a direct synthesis of various water-soluble cis-stereoregular poly(phenylacetylene)s having a narrow molecular weight distribution, the molecular weight of which can be controlled by the initial feed ratio of the monomer to the catalyst. Moreover, the syntheses of water-soluble telechelic poly(phenylacetylene)s having various functional groups at both chain ends as well as a water-soluble block copolymer were achieved.

Development of aqueous size exclusion chromatography conditions to characterize polyzwitterion-block-N-isopropyl acrylamide copolymers.

Block copolymers that exhibit both an upper critical solution temperature and a lower critical solution temperature are difficult to characterize due to inherent solubility difference between the two blocks. For example, accurate determination of both the molar mass and molar mass distribution is challenging for polyzwitterion-block-N-isopropyl acrylamide (NIPAM) copolymers in aqueous solutions due to self-assembly. However, there are a few examples of using size exclusion chromatography (SEC) for characterization, in which hexafluoro isopropanol (HFIP) is used in all cases. Yet, researchers are hesitant to use this solvent due to how expensive and hazardous HFIP is. Therefore, alternatives to HFIP for SEC analysis would be desirable. Here, a systematic methodology featuring aqueous SEC is demonstrated using several solvent conditions to enable the elution of polyzwitterion-block-NIPAM copolymers on Agilent PolarGel† and Tosoh TSKgel† column sets. These SEC conditions include 0.2M KI in water on the PolarGel columns and 0.2M KI/ 30% DMF in water on the PolarGel and TSKgel columns. These aqueous systems can be utilized for the characterization of similar water-soluble block copolymers that are relevant for drug delivery and other biomedical applications.

Highly Effective and Safe Polymeric Inhibitors of Herpes Simplex Virus in Vitro and in Vivo.

A series of poly(ethylene glycol)-block-poly(3-(methacryloylamino)propyl trimethylammonium chloride) (PEG-b-PMAPTAC) water-soluble block copolymers consisting of PEG and PMPTAC were obtained by reversible addition-fragmentation chain-transfer (RAFT) polymerization and demonstrated to function as highly effective herpes simplex virus type 1 (HSV-1) inhibitors as shown by in vitro tests (Vero E6 cells) and in vivo experiments (mouse model). Half-maximal inhibitory concentration (IC50) values were determined by quantitative polymerase chain reaction to be 0.36 ± 0.08 μg/mL for the most effective polymer PEG45-b-PMAPTAC52 and 0.84 ± 1.24 μg/mL for the less effective one, PEG45-b-PMAPTAC74. The study performed on the mouse model showed that the polymers protect mice from lethal infection. The polymers are not toxic to the primary human skin fibroblast cells up to the concentration of 100 μg/mL and to the Vero E6 cells up to 500 μg/mL. No systemic or topical toxicity was observed in vivo, even with mice treated with concentrated formulation (100 mg/mL). The mechanistic studies indicated that polymers interacted with the cell and blocked the formation of the entry/fusion complex. Physicochemical and biological properties of PEGx-b-PMAPTACy make them promising drug candidates.

A novel luminescent sensor for disaccharide detection in food: Synthesis and application of a water-soluble rod-coil ionic block copolymer

A simple and low cost method for detecting disaccharide in food product is important for people who need control the consumption of saccharides in daily life. In this study, a water soluble rod-coil ionic block copolymer poly[2,7-(9,9-dihexyl-fuorene)]-b-cationic quaternized-poly[2-(dimethylamino)ethyl methacrylate] (PF-b-PDI) was employed as luminescent sensor for detection of lactose, sucrose and maltose in food. It was found that the PF-b-PDI could emit vision fluorescence with the existence of hydroquinone (HQ) in aqueous, but would be quenched by the oxidization of hydrogen peroxide (H2O2). The glucose oxidase (GOx) could be used for catalyzing the glucose to generate the H2O2. And the sucrase, maltase and lactase could respectively catalyze sucrose, maltose and lactose to glucose. With the selectivity and catalyst of enzyme, the PF-b-PDI aqueous blend with HQ showed fluorescence sensitive to sucrose, maltose and lactose with detection limit value of 1.36 μM, 1.09 μM and 3.08 μM, respectively. Moreover, the detection of lactose in milk samples by this method just revealed 0.44% of average deviation compared to standard lactose solution, which mean this method was suitable for detecting lactose in milk.

Poly(ethylene glycol) brush-b-poly(N-vinylpyrrolidone)-based double hydrophilic block copolymer particles crosslinked via crystalline α-cyclodextrin domains.

Self-assembly of block copolymers is a significant area of polymer science. The self-assembly of completely water-soluble block copolymers is of particular interest, albeit a challenging task. In the present work the self-assembly of a linear-brush architecture block copolymer, namely poly(N-vinylpyrrolidone)-b-poly(oligoethylene glycol methacrylate) (PVP-b-POEGMA), in water is studied. Moreover, the assembled structures are crosslinked via α-CD host/guest complexation in a supramolecular way. The crosslinking shifts the equilibrium toward aggregate formation without switching off the dynamic equilibrium of double hydrophilic block copolymer (DHBC). As a consequence, the self-assembly efficiency is improved without extinguishing the unique DHBC self-assembly behavior. In addition, decrosslinking could be induced without a change in concentration by adding a competing complexation agent for α-CD. The self-assembly behavior was followed by DLS measurement, while the presence of the particles could be observed via cryo-TEM before and after crosslinking.

Reductively Responsive Gel Capsules Prepared Using a Water-Soluble Zwitterionic Block Copolymer Emulsifier.

Utilizing the unique solubility of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), which is soluble in only water and alcohol, we synthesized a water-soluble block copolymer emulsifier composed of a hydrophilic PMPC block and an amphiphilic poly[oligo(ethylene glycol) methacrylate] (POEGMA) block via reversible addition-fragmentation chain transfer (RAFT) polymerization. Water-in-oil (W/O) emulsions were successfully formed in the presence of the resulting PMPC- b-POEGMA, which acted as a stabilizer of water droplets in a chloroform continuous phase because the PMPC and POEGMA blocks were distributed to the water and chloroform phases, respectively. Next, the amphiphilic poly[poly(ethylene glycol) methacrylate] (PPEGMA) gel layer, which contained bis(2-methacryloyl)oxyethyl disulfide as a reductively responsive cross-linker, was prepared by inverse miniemulsion periphery RAFT polymerization from the PMPC- b-POEGMA that stabilized the W/O emulsions. The resulting PPEGMA gel capsules were colloidally stable in not only chloroform but also water without additional hydrophilic surface modification. The drug-release behavior from the PPEGMA gel capsules in response to dithiothreitol (DTT), which is a reducing agent, was investigated using fluorescein-conjugated dextran (FITC-Dex) as a model drug. The FITC-Dex release rate from the gel capsules in a phosphate buffer solution (pH 7.4, 20 mM) with DTT was fast compared to that without DTT. The reductively responsive FITC-Dex release is attributed to the cleavage of disulfide bonds that act as cross-links in the PPEGMA gel layer. The fascinating properties of the PPEGMA gel capsules suggest that they can provide a useful platform for designing drug carriers for protein and gene delivery and nanobioreactors.

(Invited) Reducing-Environment-Responsive Gel Capsules Prepared Via Inverse Miniemulsion Periphery RAFT Polymerization from Water-Soluble Emulsifier Stabilizing W/O Emulsions

Nano and micron-sized capsules having an inner water phase, such as liposomes and polymersomes, have been extensively studied as drug carriers because they can load water-soluble protein drugs. However, they have a few disadvantages of low mechanical strength and low loading efficiency of drugs. Therefore, the preparation of stable capsules having an inner water phase is required for constructing carriers for water-soluble protein drugs. In this study, the gel capsules consisting of an amphiphilic capsule membrane and an inner water phase were strategically prepared via inverse miniemulsion periphery reversible addition fragmentation chain transfer (RAFT) polymerization. This paper also describes the release of encapsulated model drugs from the gel capsules in response to a reducing environment. A water-soluble block copolymer emulsifier composed of PMPC block as a hydrophilic component and an amphiphilic poly[oligo(ethylene glycol) methacrylate] (POEGMA) block as a lipophilic component was synthesized via RAFT polymerization. The 1H NMR and gel permeation chromatography measurements revealed that the synthesized PMPC-b-POEGMA had 22 repeating units of PMPC and 171 repeating units of POEGMA with a narrow molecular weight distribution. The water-in-oil (W/O) emulsions were successfully formed by sonication of the water-chloroform mixture containing the resulting PMPC-b-POEGMA, which acted as a stabilizer of water droplets in a chloroform continuous phase because the PMPC and POEGMA blocks were distributed to the water and chloroform phases, respectively. The concentration of the PMPC-b-POEGMA emulsifier affected the droplet size and colloidal stability of the W/O emulsions, which was a similar attribute of conventional surfactants. The optimization of the PMPC-b-POEGMA concentration revealed that the 10 % (w/v) (relative to dispersed phase) of the PMPC-b-POEGMA emulsifier was suitable for the formation of W/O emulsions when chloroform and water were used as a continuous and a dispersed phase, respectively. Next, the amphiphilic poly[poly(ethylene glycol) methacrylate] (PPEGMA) gel layer, which contained bis(2-methacryloyl)oxyethyl disulfide (BMOD) as a reducing-environment-responsive crosslinker, was prepared by inverse miniemulsion periphery RAFT polymerization from the PMPC-b-POEGMA that stabilized the W/O emulsions. The resulting PPEGMA gel capsules were colloidally stable in not only chloroform but also water without additional hydrophilic surface modification because of the amphiphilicity of their gel capsule layer. The PPEGMA gel capsules were taken up by L929 cells with low cytotoxity. Furthermore, the drug-release behavior from the PPEGMA gel capsules in response to dithiothreitol (DTT), which is a reducing agent, was investigated using fluorescein-conjugated dextran (FITC-Dex) as a model drug. The FITC-Dex release rate from the gel capsules in a phosphate buffer (PB) solution (pH 7.4, 20 mM) with DTT was fast compared to that without DTT. When the BMOD-based crosslinks, which contain disulfide bonds, in the PPEGMA gel capsules layer are cleaved in a PB solution with DTT, a decrease in the crosslinking density of the layer induced an increase in the diffusion coefficient of FITC-Dex within the gel capsule layer. Therefore, the FITC-Dex release from the PPEGMA gel capsules was enhanced under a reducing environment. Although the application of PPEGMA gel capsules as smart drug carriers require further research regarding their structural change in response to reducing environments and controlling the drug release rate, the smart functions of the gel capsules can provide useful platforms for constructing a drug carrier that can deliver water-soluble drugs, such as low-molecular-weight drugs, proteins, and DNAs into the cytosol, which has a reducing environment. Figure 1

RAFT Polymerization of an Intrinsically Stretchable Water-Soluble Block Copolymer Scaffold for PEDOT.

Despite the common association of π-conjugated polymers with flexible and stretchable electronics, these materials can be rigid and brittle unless they are designed otherwise. For example, low modulus, high extensibility, and high toughness are treated as prerequisites for integration with soft and biological structures. One of the most successful and commercially available organic electronic materials is the conductive and brittle polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS). To make this material stretchable, additives such as ionic liquids must be used. These additives may render the composite incompatible with biological tissue. In this work, we describe the synthesis of an intrinsically stretchable variant of the conductive polymer PEDOT:PSS that is free of additives. The approach involves the synthesis of a block copolymer comprising soft segments of poly(polyethylene glycol methyl ether acrylate) (PPEGMEA) and hard segments of poly(styrene sulfonate) (PSS) using a reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, we used the newly synthesized ionic elastomer PSS-b-PPEGMEA as a matrix for the oxidative polymerization of EDOT. The resulting polyelectrolyte elastomer, PEDOT:PSS-b-PPEGMEA, can withstand elongations up to 128% and has a toughness up to 10.1 MJ m-3. While the polyelectrolyte elastomer is not as conductive as the commercial material, the toughness and extensibility are each more than an order of magnitude higher. Moreover, the electrical conductivity of the polyelectrolyte elastomer exhibits minimal decrease with strain within the elastic regime. We then compared the block copolymer to physical blends of PEDOT:PSS and PPEGMEA. The blend material had a much lower failure strain of only 38% and a maximum toughness of 4.9 MJ m-3. This approach thus emphasizes the importance of the covalent linking of the PSS and PPEGMEA blocks. Furthermore, we demonstrate that the conductivity of scratched films can be restored upon exposure to water.

In situ hydrogel formation for biomedical applications using acoustic cavitation from high intensity focused ultrasound

There is a growing interest in polymer mechanochemistry for their industrial applications. For example, stress-induced crosslinking gel formation from polymer networks is a rapidly growing field of study. Recent work utilizes a variety of different polymer structures and crosslinking mechanisms. However, these polymers are typically soluble in only organic solvents and require the use of a sonicating probe or bath at frequencies below 100 kHz. These requirements limit their use in biomedical applications that require in situ gel formation within a patient (e.g., blocking of varicose veins, internal wound healing, etc.). Here we report on the development of a water soluble block copolymer that forms a hydrogel in the presence of acoustic cavitation from high intensity focused ultrasound. These block copolymers are comprised of hydrophilic polyethylene glycol methyl methacrylate units and hydrophobic tridentate crosslinkers. The tridentate crosslinker forms bonds with free metal ions in solution only in the presence of acoustic cavitation induced mechanical stress. We show that the block copolymer is capable of forming a hydrogel in under 90 seconds and will also block a liquid channel formed in an agarose cylinder.

Synthesis of water soluble metalloporphyrin-cored amphiphilic star block copolymer photocatalysts for an environmental application

Two series of water-soluble metalloporphyrin-cored amphiphilic star block copolymers were synthesized by controlled radical polymerizations such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation chain transfer (RAFT), which gave eight amphiphilic block copolymer arm chains consisting of poly(n-butyl acrylate-b-poly(ethylene glycol) methyl ether methacylate) (PnBA-b-PEGMEMA, Mn,GPC = 78,000, Mw/Mn = 1.2, 70 wt% of PPEGMEMA) and poly(styrene-b-2-dimethylamino ethyl acrylate) (PS-b-PDMAEA, Mn,GPC = 83,000, Mw/Mn = 1.2, 67 wt% of PDMAEA), yielding porphyrin(Pd)-(PnBA-b-PPEGMEMA)8 and porphyrin(Pd)-(PS-b-PDMAEA)8, respectively. Obtained metalloporphyrin polymer photocatalysts were homogeneously solubilized in water to apply to the removal of chlorophenols in water, and was distinguished from conventional water-insoluble small molecular metalloporphyrin photocatalysts. Notably, we found that the water-soluble star block copolymers with hydrophobic–hydrophilic core–shell structures more effectively decomposed the chlorophenol, 2,4,6-trichlorophenol (2,4,6-TCP), in water under visible light irradiation (k = 1.39 h−1, t1/2 = 0.5 h) in comparison to the corresponding water-soluble star homopolymer, because the hydrophobic core near the metalloporphyrin effectively captured and decomposed the hydrophobic chlorophenols in water.

Side‐chain glycylglycine‐based polymer for simultaneous sensing and removal of copper(II) from aqueous medium

ABSTRACTSince glycylglycine (Gly‐Gly) residue in the N‐terminal region of human prion protein, a copper binding protein, binds with Cu(II), N‐terminus Gly‐Gly side‐chain containing water soluble block copolymer was synthesized and used for simultaneous sensing and removal of Cu(II) ion from aqueous medium. The polymer has amide nitrogen atom and ester carbonyl group as potential binding sites in the side‐chain Gly‐Gly pendants. Job's plot experiment confirms 2:1 binding stoichiometry of polymer with Cu(II). This polymer is able to sense parts per billion level of Cu(II) very selectively in an aqueous medium and remove Cu(II) ions quantitatively by precipitating out the Cu(II) via complex formation in the pH range 7–9. The binding mode of polymer with Cu(II) in polymer‐Cu(II) complex was characterized by 1H NMR, FTIR, and UV–vis spectroscopy. The attachment of Cu(II) in the polymer‐Cu(II) complex was confirmed by cyclic voltammetry experiment. Cu(II) release from the complex was achieved at pH 5 due to the protonation of amide nitrogen atoms in the Gly‐Gly moiety. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 914–921

Synthesis of block polycarboxylate copolymer and its application in a cement system

The sequence structure of polymers plays an important role in determining their performance. However, existing polycarboxylates mostly have a broad molecular weight distribution and the sequence structure is randomly distributed. In this work, a novel water-soluble block copolymer made of poly(ethylene glycol) methyl ether methacrylate (OEGMA) and acrylic acid (AA) was designed using reversible addition-fragmentation chain transfer polymerisation. Structural information of the block polycarboxylate was characterised by gel permeation chromatography and proton nuclear magnetic resonance. The effects of molar ratio of AA to OEGMA on flowability, zeta potential and adsorption in cement paste were studied. It was proved that polycarboxylate with a block distribution could be successfully applied as a superplasticiser. Furthermore, the length of the two blocks in the block distribution influenced the zeta potential and adsorption of the superplasticiser onto cement particle surfaces, and thereby the workability of cementitious materials. The knowledge gained from this work may be used in the design of superplasticisers for optimal performance in some specific applications.

Polymer-Doxorubicin Conjugate Micelles Based on Poly(ethylene glycol) and Poly(N-(2-hydroxypropyl) methacrylamide): Effect of Negative Charge and Molecular Weight on Biodistribution and Blood Clearance.

Well-defined water-soluble block copolymers poly(ethylene glycol)-b-poly(N-(2-hydroxypropyl) methacrylamide-co-N-methacryloylglycylglycine) (PEG-b-P(HPMA-co-MAGG)) and their doxorubicin (Dox) conjugates with different composition and molecular weight were synthesized. These Dox conjugates can form micelles in buffer solution. The physicochemical properties, in vivo biodistribution, blood clearance, and especially the tumor accumulation of copolymers and micelles were studied. Severe liver accumulation can be observed for PEG-b-PMAGG copolymers. This was quite different from their Dox conjugate for which decreased RES uptake and elevated kidney accumulation could be observed. When decrease the negative charge to an appropriate amount such as 8-10 mol %, both RES uptake and kidney accumulation could be suppressed. Obvious tumor accumulation could be achieved especially when the molecular weight were increased from ∼40 to ∼80 KDa. These results provided us with a guideline for the design of nanoscaled drug delivery system as well as a potential option for treating kidney-related cancers.