Atom Transfer Radical Polymerization Technology Research Articles

Bioinspired Dopamine and N-Oxide-Based Zwitterionic Polymer Brushes for Fouling Resistance Surfaces.

Biofouling is a great challenge for engineering material in medical-, marine-, and pharmaceutical-related applications. In this study, a novel trimethylamine N-oxide (TMAO)-analog monomer, 3-(2-methylacrylamido)-N,N-dimethylpropylamine N-oxide (MADMPAO), was synthesized and applied for the grafting of poly(MADMPAO) (pMPAO) brushes on quartz crystal microbalance (QCM) chips by the combination of bio-inspired poly-dopamine (pDA) and surface-initiated atom transfer radical polymerization technology. The result of ion adsorption exhibited that a sequential pDA and pMPAO arrangement from the chip surface had different characteristics from a simple pDA layer. Ion adsorption on pMPAO-grafted chips was greatly inhibited at low salt concentrations of 1 and 10 mmol/L due to strong surface hydration in the presence of charged N+ and O- of zwitterionic pMPAO brushes on the outer layer on the chip surface, well known as the "anti-polyelectrolyte" effect. During BSA adsorption, pMPAO grafting also led to a marked decrease in frequency shift, indicating great inhibition of protein adsorption. It was attributed to weaker BSA-pMPAO interaction. In this study, the Au@pDA-4-pMPAO chip with the highest coating concentration of DA kept stable dissipation in BSA adsorption, signifying that the chip had a good antifouling property. The research provided a novel monomer for zwitterionic polymer and demonstrated the potential of pMPAO brushes in the development and modification of antifouling materials.

Strong and robust cellulose-based enzymatic membrane with gradient porous structure in dynamically catalytic removal of sulfonamides antibiotics

Enzyme membrane systems (EMS) have generated considerable interest because of their advantages of accelerating reactions, eliminating product inhibition, and enhancing conversion rates. However, there are deficiencies in the efficient fabrication of affinity carrier membranes and dynamic catalytic separation properties. Herein, a strong and highly flexible spunlaced viscose/bacterial cellulose (BC) composite membrane in situ embedded with graphene oxide (GO) was developed by combining a scalable bio-synthesis method with atom transfer radical polymerization technology. Notably, the layer-by-layer growth of BC on composite film and the addition of GO resulted in an entangled network with strong hydrogen bonding, endowing the resulting membrane with superior mechanical properties and flexibility, while facilitating a gradient structure and porous transport channels. Subsequently, a novel and highly efficient EMS was constructed by using abundant molecular brushes on composite membrane as immobilized enzyme carrier. The resulting EMS exhibited a high throughput (2.17 L/min*m2) and an interception rate (98.64%) in dynamic catalytic sulfonamide antibiotic wastewater activated with syringaldehyde mediator. Meanwhile, the removal rates of sulphapyridine and sulfamethazine were 97.20% and 94.78% under 0.14 MPa and 15 min, respectively. This efficient and scalable manufacturing strategy is of great significance and may pave a novel pathway for antibiotics wastewater treatment and recycling.

Toward Green Atom Transfer Radical Polymerization: Current Status and Future Challenges.

Reversible‐deactivation radical polymerizations (RDRPs) have revolutionized synthetic polymer chemistry. Nowadays, RDRPs facilitate design and preparation of materials with controlled architecture, composition, and functionality. Atom transfer radical polymerization (ATRP) has evolved beyond traditional polymer field, enabling synthesis of organic–inorganic hybrids, bioconjugates, advanced polymers for electronics, energy, and environmentally relevant polymeric materials for broad applications in various fields. This review focuses on the relation between ATRP technology and the 12 principles of green chemistry, which are paramount guidelines in sustainable research and implementation. The green features of ATRP are presented, discussing the environmental and/or health issues and the challenges that remain to be overcome. Key discoveries and recent developments in green ATRP are highlighted, while providing a perspective for future opportunities in this area.

Reusable Surface-Modified Bacterial Cellulose Based on Atom Transfer Radical Polymerization Technology with Excellent Catalytic Properties.

The high catalytic activity of membrane-binding gold nanoparticles (AuNPs) makes its application in oxidation or reduction an attractive challenge. Herein, surface-functionalized bacterial cellulose (BC-poly(HEMA)) was successfully prepared with 2-hydroxyethyl methacrylate (HEMA) as monomers via the atom transfer radical polymerization (ATRP) method. BC-poly(HEMA) was further utilized as not only reducing agent but also carrier for uniform distribution of the AuNPs in the diameter of about 8 nm on the membrane surface during the synthesis stage. The synthesized AuNPs/BC-poly(HEMA) exhibited excellent catalytic activity and reusability for reducing 4-nitrophenol (4-NP) from NaBH4. The results proved that the catalytic performance of AuNPs/BC-poly(HEMA) was affected by the surrounding temperature and pH, and AuNPs/BC-poly(HEMA) maintained the extremely high catalytic activity of AuNPs/BC-poly(HEMA) even after 10 reuses. In addition, no 4-NP was detected in the degradation solution after being stored for 45 days. The reusable catalyst prepared by this work shows a potential industrial application prospect.

Polydopamine-Based Tumor-Targeted Multifunctional Reagents for Computer Tomography/Fluorescence Dual-Mode Bioimaging-Guided Photothermal Therapy.

Development of multifunctional diagnosis and treatment reagents is very meaningful in clinical application. Herein, we developed a polydopamine-based (PDA-based) tumor targeted multifunctional reagent by surface-initiated atom transfer radical polymerization (ATRP) strategy. First, the targeted PDA nanoparticles were prepared via combining with folic acid (FA) and dopamine. Then ATRP technology was used to graft the europium(III) complexes onto PDA surface (defined as FEDA). A series of detections revealed that the FEDA nanoparticles had been successfully prepared and exhibited a bright X-ray computer tomography (CT) and photoluminescence (PL) dual-mode imaging efficiency and an excellent photothermal therapy (PTT) effect in vivo/in vitro.

Preparation of novel polyamine-type chelating resin with hyperbranched structures and its adsorption performance.

This paper explored the method of combining atom transfer radical polymerization (ATRP) technology and hyperbranched polymer principle to prepare the high capacity chelating resin. First, surface-initiated atom transfer radical polymerization (SI-ATRP) method was used to graft glycidyl methacrylate (GMA) on chloromethylated cross-linked styrene-divinylbenzene resin, and then the novel polyamine chelating resin with a kind of hyperbranched structure was prepared through the amination reaction between amino group of (2-aminoethyl) triamine and epoxy group in GMA. This resin had a selective effect on As(V) and Cr(VI) at a relatively low pH and can be used for the disposal of waste water containing As(V) and Cr(VI). It had a relatively strong adsorption effect on Cu(II), Pb(II), Cd(II) and Cr(III) and can be used for the disposal of heavy metal ion waste water. The finding was that, the adsorption capacity of resin on the studied heavy metal ions was higher than that of the chelating resin synthesized by traditional technology and also higher than that of the resin modified by ATRP technology and bifunctional chelator, indicating that the combination of ATRP and hyperbranched polymer concept is an effective method to prepare chelating resin with high capacity.

Influence of brush length of PVP chains immobilized on silicon wafers on their blood compatibility

In this study, the influence of variations in chain length of polyvinylpyrrolidone (PVP) brushes on the blood compatibility of silicon wafer surfaces to which they were chemically attached was studied. Si surfaces were functionalized with various lengths of PVP brush using atom transfer radical polymerization technology and confirmed by elliptical polarized light, atom force microscopy, and X‐ray photoelectron spectroscopy. The blood compatibility of these biointerfaces were systematically investigated by measuring protein adsorption, clotting time, platelet adhesion, contact activation, and complement activation. The results indicate that the hemocompatibility of the surfaces was highly related to PVP brush chain length and hydrophilicity of the surfaces. Our results contribute to rational biointerface design for specific biomedical applications. The results reveal that the PVP brushes with a long chain length have great potential for blood contacting applications due to their reduced protein absorption and cell activation following its contact with blood.

Bio‐inspired synthesis of molecularly imprinted nanocomposite membrane for selective recognition and separation of artemisinin

ABSTRACTInspired from the highly bioadhesive performance of mussel protein, a simple, yet efficient synthetic method for efficiently imprinting of Artemisinin (Ars) was developed to prepare the bio‐inspired molecularly imprinted membranes (MIMs) via atom transfer radical polymerization (ATRP). In this work, attributed to the unique properties of polydopamine (pDA) modified layers and ATRP technology, the uniform recognition sites for efficiently selective extraction of the Ars with high stability could be obtained on the MIMs surfaces. In addition, the maximum adsorption capacity of the MIMs is 158.85 mg g−1 by the Langmuir isotherm model, which is remarkable higher than NIMs. Additionally, because of the formation of the uniform specific recognition cavities on membrane surfaces, the as‐prepared MIMs exhibited a rapid adsorption dynamics and well‐fitted for the pseudo‐second‐order rate equation, also, possessed an excellent per‐selectivity performance (βartemether/Ars values is 0.18) of template molecule, which clearly demonstrated the potential value of this method in the selective separation and purification of Ars. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43405.

A Straightforward Method for Preparing Well-Defined Responsive Diselenide-Containing Polymers Based on ATRP.

Diselenide-containing polymers are facilely synthesized from polymers prepared by atom transfer radical polymerization (ATRP). Benefiting from the ATRP technology, this protocol provides a flexible route for controlling the polymer structure, which allows for a great variety of architectures of selenium-containing polymer materials for applications in various fields. The oxidative and reductive responsive behavior of the obtained diselenide-containing polymers is also investigated.