\Preparation of poly(styrene-co-acrylic acid)-zinc oxide composites: Experimental and theoretical investigation of gamma radiation shielding properties.

This study, it is aimed to prepare a polymer composite between styrene, acrylic acid, and ZnO and to measure the radiation shielding of the synthesized polymer composite. Firstly poly(styrene-co-acrylic acid) (P(S-co-AA)) copolymer was synthesized using the emulsion polymerization method between styrene and acrylic acid. Then, P(S-co-AA)-ZnO composites were prepared with different percentages of ZnO. For preparing these composites, the materials were mixed in a 60 °C ultrasonic bath. P(S-co-AA)-ZnO was poured into Petri dishes to form a film. When the TG curves were examined, it was not found a significant difference between the copolymer composite and the copolymer. The molecular weight of the copolymer was found to be 120000. SEM images show zinc fragments located between the polymer chains. The potential for radiation capture against gamma was determined using a NaI scintillation detector. The linear gamma attenuation coefficients for P(S-co-AA)-ZnO samples were calculated to Lambert's Beer Law and measured for 662 keV. Theoretical gamma attenuation coefficient values were calculated by multiplying the density of the composite with the mass attenuation coefficients. The absorption parameters of polymer composites are directly proportional to the increasing amount of zinc oxide. P(S-co-AA)-ZnO-15% was the best absorber at 662 keV energy compared to other polymer composites.

Living Anionic Addition Reaction of 1,1-Diphenylethylene Derivatives: One-Pot Synthesis of ABC-type Chain-End Sequence-Controlled Polymers.

In this study, a 1:1 addition reaction using 1,1-diphenylethylene (DPE) derivatives, referred to as the "living anionic addition reaction", was established to regulate the sequence of vinyl compounds having negligible homopolymerizability. The stoichiometric and successive addition reaction between a DPE anion and more reactive DPE derivatives proceeded quantitatively when the electrophilicity of the DPE derivatives was sufficiently enhanced by electron-withdrawing groups such as (trimethylsilyl)ethynyl and acyl groups. The relative electrophilicity of the DPE derivatives was predicted by Hammett's law and the ß-carbon chemical shifts of the carbon-carbon double bonds. AB- and ABC-type chain-end sequence-controlled polystyrenes with well-defined structures were synthesized by reacting two or three DPE derivatives with difunctional anionic living polystyrene in increasing order of their electrophilicity in a one-pot reaction.

Amphiphilic Nitroxide-Bearing Siloxane-Based Block Copolymer Coatings for Enhanced Marine Fouling Release.

The buildup of organic matter and organisms on surfaces exposed to marine environments, known as biofouling, is a disruptive and costly process affecting maritime operations. Previous research has identified some of the surface characteristics particularly suited to the creation of antifouling and fouling-release surfaces, but there remains room for improvement against both macrofouling and microfouling organisms. Characterization of their adhesives has shown that many rely on oxidative chemistries. In this work, we explore the incorporation of the stable radical 2,2,6,6-tetramethylpipiderin-1-oxyl (TEMPO) as a component in an amphiphilic block copolymer system to act as an inhibitor for marine cements, disrupting adhesion of macrofouling organisms. Using polystyrene-b-poly(dimethylsiloxane-r-vinylmethysiloxane) block copolymers, pendent vinyl groups were functionalized with TEMPO and poly(ethylene glycol) to construct an amphiphilic material with redox active character. The antifouling and fouling-release performance of these materials was investigated through settlement and removal assays of three model fouling organisms and correlated to surface structure and chemistry. Surfaces showed significant antifouling character and fouling-release performance was increased substantially toward barnacles by the incorporation of stable radicals, indicating their potential for marine antifouling applications.

Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers.

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46-58 nm and periodicities of 70-102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.

Preparation of poly(sodium 4-styrene sulfonate) grafted magnetic chitosan microspheres for adsorption of cationic dyes.

A novel adsorbent with high adsorption capacity to remove cationic dyes was synthesized. Sodium 4-styrene sulfonate (SSS) was grafted polymerization on the surface of magnetic chitosan microspheres via -NH2/S2O82- surface initiating system, obtaining MCS-g-PSSS microspheres. The grafted microsphere was characterized by Fourier transforms infrared spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, vibration sample magnetometer and the Brunauer-Emmett-Teller. Cationic dyes were adsorbed by MCS-g-PSSS and methylene blue(MB) was acted as a typical example. The adsorption performance was explored by varying experimental conditions. The results showed the maximal adsorption capacity was 989 mg/g at pH 1 at 25 °C. The pseudo-second order model was found to be applicable for the adsorption kinetics. The adsorption capacity increased with rising temperature and it decreased owing to adding of ions. The adsorption isotherms were the best fitted by Langmuir. MCS-g-PSSS for MB showed high adsorption capacity due to the strong electrostatic interactions and π-π stacking, which was explained by FTIR and XPS and was verified by DFT calculations. The degree of adsorption spontaneity increased with rising the temperature. The grafted MCS-g-PSSS microspheres had high adsorption capacity for various kinds of cationic dyes and excellent for remove MB in the aqueous solution.

Mesoporous knitted inverse vulcanised polymers.

Elemental sulfur is generated in large quantities when crude oil is refined. This elemental sulfur has limited use other than the production of sulfuric acid. Recently, the development of 'inverse vulcanised' polymers has attracted the attention of researchers. These polymers are formed from elemental sulfur and a small molecule alkene. The affinity of sulfur for heavy metals gives these polymers potential for specific adsorption; however, there is a lack of incorporation of high specific surface areas in pure polymers. Herein, we report the first mesoporous polymer generated using inverse vulcanised polymers, with a BET surface area of 236.04 m2 g-1. We explore the properties of polymers as an absorption medium for potent neurotoxin Hg(ii).

Protein Adsorption on Surfaces Functionalized with COOH Groups Promotes Anti-inflammatory Macrophage Responses.

Implants can induce a foreign body reaction that leads to chronic inflammation and fibrosis in the surrounding tissue. Macrophages help detect the foreign material, play a role in the inflammatory response, and may promote fibrosis instead of the desired tissue regeneration around implants. Implant surface properties impact macrophage responses by changing the nature of the adsorbed protein layer, but conflicting studies highlight the complexity of this relationship. In this study, the effect of surface chemistry on macrophage behavior was investigated with poly(styrene) surfaces containing common functional groups at similar surface densities. The protein layer was characterized to identify the proteins that adsorbed on the surfaces from the medium and the proteins secreted onto the surfaces by adherent macrophages. Of the surface chemistries studied, carboxylic acid (COOH) groups promoted anti-inflammatory responses from unstimulated macrophages and did not exacerbate inflammation upon stimulation. These surfaces also enhanced the adsorption of proteins involved in integrin signaling and promoted the secretion of proteins related to angiogenesis, integrin signaling, and cytokine signaling, which have been previously associated with improved biomaterial integration. Therefore, this study suggests that surface modification with COOH groups may help improve the integration of implants in the body by enhancing anti-inflammatory macrophage responses through altered protein adsorption.

Shape-transformation of polymersomes from glassy and crosslinkable ABA triblock copolymers.

Recent developments in the field of polymer vesicles, i.e. polymersomes, have demonstrated that disrupting the equilibrium conditions of the milieu could lead to shape transformation into stable non-spherical morphologies, bringing on-demand shape control to reality and bearing great promise for cell mimicry and a variety of biomedical applications. Here, we studied the self-assembly behavior of glassy amphiphilic triblock copolymers, poly(ethylene glycol)-block-polystyrene-stat-poly(coumarin methacrylate)-block-poly(ethylene glycol) (PEG-b-P(S-stat-CMA)-b-PEG), and their response to various stimuli. By changing the respective molecular weights of both the hydrophobic P(S-stat-CMA) and the hydrophilic PEG blocks, we varied the hydrophobic volume fraction thereby accessing a range of morphologies from spherical and worm-like micelles, as well as polymersomes. For the latter, we observed that slow osmotic pressure changes induced by dialysis led to a decrease in size while rapid osmotic pressure changes by addition of a PEG fusogen led to morphological transformations into rod-like and tubular polymersomes. We also found out that chemically crosslinking the vesicles before inducing osmotic pressure changes led to the vesicles exhibiting hypotonic shock, atypical for glassy polymersomes. We believe that this approach combining the robustness of triblock copolymers and light-based transformations will help expand the toolbox to design ever more complex biomimetic constructs.

Native nanodiscs formed by styrene maleic acid copolymer derivatives help recover infectious prion multimers bound to brain-derived lipids.

Prions are lipidated proteins that interact with endogenous lipids and metal ions. They also assemble into multimers and propagate into the infectious scrapie form known as PrPSc The high-resolution structure of the infectious PrPSc state remains unknown, and its analysis largely relies on detergent-based preparations devoid of endogenous ligands. Here we designed polymers that allow isolation of endogenous membrane:protein assemblies in native nanodiscs without exposure to conventional detergents that destabilize protein structures and induce fibrillization. A set of styrene-maleic acid (SMA) polymers including a methylamine derivative facilitated gentle release of the infectious complexes for resolution of multimers, and a thiol-containing version promoted crystallization. Polymer extraction from brain homogenates from Syrian hamsters infected with Hyper prions and WT mice infected with Rocky Mountain Laboratories prions yielded infectious prion nanoparticles including oligomers and microfilaments bound to lipid vesicles. Lipid analysis revealed the brain phospholipids that associate with prion protofilaments, as well as those that are specifically enriched in prion assemblies captured by the methylamine-modified copolymer. A comparison of the infectivity of PrPSc attached to SMA lipid particles in mice and hamsters indicated that these amphipathic polymers offer a valuable tool for high-yield production of intact, detergent-free prions that retain in vivo activity. This native prion isolation method provides an avenue for producing relevant prion:lipid targets and potentially other proteins that form multimeric assemblies and fibrils on membranes.

Development of Molecularly Imprinted 2D Photonic Crystal Hydrogel Sensor for Detection of L-Kynurenine in Human Serum.

l-Kynurenine (KYN) is a metabolite of the Kynurenine pathway and is a known potential marker of immune suppressant disorders and cancer. Here, we present a molecularly imprinted two dimensional (2D) Photonic crystal (PC) hydrogel sensor for the detection of L-KYN in human serum. The sensor utilizes polystyrene-based 2D PC colloidal arrays (2D PCCA) hydrogel with methacrylic acid as the functional monomer which can imprint the L-KYN template by hydrogen bonding. After removal of the template, the resulting nanocavities in the hydrogel can selectively bind and recognize L-KYN in the serum samples. The binding is selective for L-KYN, which is revealed by shrinkage of the hydrogel volume and decrease in the particle spacing that can be easily monitored through changes in the Debye diffraction ring diameter using a LASER pointer. The sensor demonstrates visible red to green color shift upon binding to L-KYN. The 2D PC sensor demonstrates the limit of detection (LOD) of 50  nM, linear relationship of particle spacing versus L-KYN concentration range (50-1000  nM) with the analytical recovery of up to 92 % in the spiked serum samples. The sensor can distinguish between L-KYN and D-KYN and is re-usable up to five times. The sensor is available for the rapid and quantitative detection of L-KYN in the human serum.

Metal-Encoded Polystyrene Microbeads as a Mass Cytometry Calibration/Normalization Standard Covering Channels from Yttrium (89 amu) to Bismuth (209 amu).

Mass cytometry (MC) measures metal isotope signals from single cells and bead samples. Since large numbers of isotopes can be employed as labels, mass cytometry is a powerful analytical technique for multiparameter cytometric assays. The calibration protocol in MC is a critical algorithm, which employs metal-encoded microbeads as an internal standard to correct the data for instrumental signal drift. The current generation of commercially available beads carries four lanthanide elements (cerium, europium, holmium, and lutetium). However, this is not sufficient to calibrate the full span of detection channels, ranging from yttrium (89 amu) to bismuth (209 amu), which are now available. To address this issue we prepared polystyrene microbeads encoded with seven elements (yttrium, indium, and bismuth in addition to the four lanthanides) by multistage dispersion polymerization for MC calibration and normalization. The bead synthesis conditions were optimized to obtain microbeads that were uniform in size and generated strong MC signal intensities at similar levels for the eight encoded isotopes. Metal ion leaching from the beads under storage and application conditions was also examined. We demonstrated that the precision of normalized MC signals in the MC detection channels was improved by employing seven-element-encoded microbeads as a standard.

Metal-Chelated Polymer Nanodiscs for NMR Studies.

Paramagnetic relaxation enhancement (PRE) is commonly used to speed up spin lattice relaxation time (T1 ) for rapid data acquisition in NMR structural studies. Consequently, there is significant interest in novel paramagnetic labels for enhanced NMR studies on biomolecules. Herein, we report the synthesis and characterization of a modified poly(styrene-co-maleic acid) polymer which forms nanodiscs while showing the ability to chelate metal ions. Cu2+ -chelated nanodiscs are demonstrated to reduce the T1 of protons for both polymer and lipid-nanodisc components. The chelated nanodiscs also decrease the proton T1 values for a water-soluble DNA G-quadruplex. These results suggest that polymer nanodiscs functionalized with paramagnetic tags can be used to speed-up data acquisition from lipid bilayer samples and also to provide structural information from water-soluble biomolecules.

Wolf-Lamb-type Catalysis in One Pot Using Electrospun Polymeric Catalyst Membranes.

Multistep catalytic transformations using incompatible catalysts (Wolf-Lamb-type) in a one-pot reaction cascade require site isolation of different catalysts by compartmentalization. In this work, the use of different electrospun catalytic membranes in a modular way as individual compartments is shown for one-pot Wolf-Lamb-type reaction cascades. The data are presented for one-pot cascade reaction sequences catalyzed by acidic and basic membranes made by electrospinning polymeric acid (poly(styrene-co-styrene sulfonic acid-co-4-methacryloyl-oxybenzophen)) and basic (poly(styrene-co-4-vinylpyridine-co-4-methacryloyl-oxybenzophen)) catalysts, respectively. The two-step, one-pot system used is the acidic catalyzed deacetylation of dimethoxybenzylacetale to benzaldehyde, which reacts with ethyl cyanoformate to result in a high yield of product (over 90%) under base-catalyzed conditions. The reaction kinetics are further monitored and evaluated by using differential equations, showing the necessity of a parameter Δt to represent a retarded start for the second reaction step. The concept provides an easy and upscalable approach for use in Wolf-Lamb-type systems.

Phthalocyanine-doped polystyrene fluorescent nanocomposite as a highly selective biosensor for quantitative determination of cancer antigen 125.

A novel, simple, sensitive, and precise spectrofluorometric assay of cancer antigen [CA 125] is described. This modality is based on monitoring the quenching of the luminescence intensity at 790 nm of the phthalocyanine fluorophore, in a nanocomposite comprising the fluorophore and cationic polystyrene, which results from interaction with CA 125. The remarkable quenching of the luminescence intensity of the Ni-phthalocyanine complex doped in PS matrix by various concentrations of CA 125 was successfully utilized as an optical sensor for the determination of CA 125 in different serum samples of ovarian disease. The performance of the designed biosensor is determined through monitoring the quenching of the luminescence intensity at 790 nm by cancer antigen 125 after excitation at 685 nm, pH 7.3 in water. The calibration plot was achieved over the concentration range 1.0 × 10-2 - 127 U mL-1 CA-125 with a correlation coefficient of 0.99 and detection limit of 1.0 × 10-4 U mL-1. The mechanism of the interaction between the nano thin film nickel(II)phthalocyanine and CA-125 was discussed. A significant correlation between the proposed method for the assessment of CA 125 and the standard method was applied to patients and controls.

Radical polymerization inside living cells.

Polymerization reactions conducted inside cells must be compatible with the complex intracellular environment, which contains numerous molecules and functional groups that could potentially prevent or quench polymerization reactions. Here we report a strategy for directly synthesizing unnatural polymers in cells through free radical photopolymerization using a number of biocompatible acrylic and methacrylic monomers. This offers a platform to manipulate, track and control cellular behaviour by the in cellulo generation of macromolecules that have the ability to alter cellular motility, label cells by the generation of fluorescent polymers for long-term tracking studies, as well as generate a variety of nanostructures within cells. It is remarkable that free radical polymerization chemistry can take place within such complex cellular environments. This demonstration opens up a multitude of new possibilities for how chemists can modulate cellular function and behaviour and for understanding cellular behaviour in response to the generation of free radicals.

Highly Stable and Luminescent Oxygen Nanosensor Based on Ruthenium-Containing Metallopolymer for Real-Time Imaging of Intracellular Oxygenation.

Metal complex-based luminescent oxygen nanosensors have been intensively studied for biomedical applications. In terms of monitoring dynamics of intracellular oxygen, however, high-quality nanosensors are still badly needed, because of stringent requirements on stability, biocompatibility and luminescence intensity, aside from oxygen sensitivity. In this paper, we reported a type of highly luminescent and stable oxygen nanosensors prepared from metallopolymer. First, a novel ruthenium(II)-containing metallopolymer was synthesized by chelating the oxygen probe [Ru(bpy)3]2+ with a bipyridine-branched hydrophobic copolymer, which was then doped into polymeric nanoparticles (NPs) by a reprecipitation method, followed by further conjugation to selectively target mitochondria (Mito-NPs). The resultant Mtio-NPs possessed a small hydrodynamic size of ∼85 nm, good biocompatibility and high stability resulting from PEGylation and stable nature of Ru-complex. Because the complexed [Ru(bpy)3]2+ homogeneously resided on particle surface, Mito-NPs exhibited strong luminescence at 608 nm that was free of aggregation-caused-quenching, the utmost oxygen sensitivity of free [Ru(bpy)3]2+ probe ( Q = 75%), and linear Stern-Volmer oxygen luminescence quenching plots. Taking advantage of the mitochondria-specific nanosensors, intracellular oxygenation and deoxygenation processes were real-time monitored for 10 min by confocal luminescence imaging, visualized by the gradual weakening (by more than 90%) and enhancing (by 50%) of the red emission, respectively.

Tough hydrophobic association hydrogels with self-healing and reforming capabilities achieved by polymeric core-shell nanoparticles.

The application range of hydrogels can be greatly widened by improving their mechanical properties. It is still a great challenge to develop hydrogels with good mechanical properties, reliable self-healing properties and remolding ability at the same time. Inspired by biological soft tissue with excellent mechanical properties and self-healing properties, here, a facile method to fabricate poly (styrene-acrylic acid) (P(S-AA)) core-shell nanoparticles with plenty of carboxyl groups on their surface, and their enhancement to hydrophobic association hydrogels was reported. Under stress, the dynamic physical bonds including hydrogen bonding between polymer chains and P(S-AA) core-shell nanoparticles (NPs), and entanglement of hydrophobic chains were destroyed to effectively dissipate energy, and uniform hydrogel network leads to smooth stress-transfer, which makes the core-shell nanoparticles composite hydrophobic association hydrogels (MHA gels) excellent mechanical properties, such as excellent mechanical properties, toughness and ductility, and good self-healing properties as well. These features make the MHA gels have great potential in biomedical applications such as tissue engineering, articular cartilage and artificial skin.

Structural characterization of styrene-maleic acid copolymer-lipid nanoparticles (SMALPs) using EPR spectroscopy.

Spectroscopic studies of membrane proteins (MPs) are challenging due to difficulties in preparing homogenous and functional lipid membrane mimetic systems into which membrane proteins can properly fold and function. It has recently been shown that styrene-maleic acid (SMA) copolymers act as a macromolecular surfactant and therefore facilitate the formation of disk-shaped lipid bilayer nanoparticles (styrene-maleic acid copolymer-lipid nanoparticles (SMALPs)) that retain structural characteristics of native lipid membranes. We have previously reported controlled synthesis of SMA block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization, and that alteration of the weight ratio of styrene to maleic acid affects nanoparticle size. RAFT-synthesis offers superior control over SMA polymer architecture compared to conventional radical polymerization techniques used for commercially available SMA. However, the interactions between the lipid bilayer and the solubilized RAFT-synthesized SMA polymer are currently not fully understood. In this study, EPR spectroscopy was used to detect the perturbation on the acyl chain upon introduction of the RAFT-synthesized SMA polymer by attaching PC-based nitroxide spin labels to the 5th, 12th, and 16th positions along the acyl chain of the lipid bilayer. EPR spectra showed high rigidity at the 12th position compared to the other two regions, displaying similar qualities to commercially available polymers synthesized via conventional methods. In addition, central EPR linewidths and correlation time data were obtained that are consistent with previous findings.

The adsorption of DNA by cationic core-shell diblock copolymer polystyrene-block-poly(N-methyl 4-vinylpyridine iodide) micelles.

The diblock copolymer polystyrene-block-poly(N-methyl 4-vinylpyridine iodide) (PS-b-P4VPQ) with the molecular weight of PS 3.5 × 103 g/mol and P4VPQ 11.6 × 103 g/mol forms core-shell polymer micelles in aqueous solution. The cationic brush shell of the polymer micelle can be used to accommodate hydrophilic drugs and biomolecules, such as DNA, for biomedical applications. It is essential to understand how biomolecules are adsorbed within the brush layer. Here we investigated the interaction of the cationic brush of the polymer micelle with DNA by small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). It is found when adding only relatively small amounts of on average 30 base pairs (bp) DNA, at 19.6 and 39.2 µM for 0.1 mM PS-b-P4VPQ, most of the polymer micelle/DNA complexes remain well dispersed. The brush layer of the polymer micelles are slightly swelled due to the adsorption of DNA within the brush layer. When the DNA concentration is increased to 58.8 µM or higher, the polymer micelle/DNA complexes form closely packed agglomerates. At high DNA concentrations, some adsorbed DNA will start to build up at the edge or surface of the brush layer which could induce aggregation of the polymer micelle/DNA complexes. This means that it is possible to prepare mostly dispersed polymer/DNA complexes by keeping the DNA concentration below the aggregation concentration. The well dispersed polymer micelle/DNA complexes are advantageous for many DNA related biomedical applications.

ICAR ATRP in PEG with Low Concentration of Cu(II) Catalyst: A Versatile Method for Synthesis of Block Copolymer Nanoassemblies under Dispersion Polymerization.

A versatile method for synthesis of block copolymer nanoassemblies via initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) dispersion polymerization in a low molecular weight poly(ethylene glycol) (PEG) is discussed. This ICAR ATRP dispersion polymerization uses a low concentration of CuBr2 catalyst, which is stable under atmospheric conditions and is soluble in most polar solvents and employs a polymerization medium of viscous and nonvolatile PEG. Through this ICAR ATRP dispersion polymerization, various block copolymer nanoassemblies, including poly(ethylene glycol)-block-polystyrene, poly(ethylene glycol)-block-poly(methyl methacrylate), and poly(2-hydroxypropyl methacrylate)-block-poly(methyl methacrylate), have been synthesized. The parameters affecting the size and morphology of the block copolymer nanoassemblies are briefly discussed.