Synthesis, characterization and application of well-defined environmentally responsive polymer brushes on the surface of colloid particles

Well-defined poly(2-(dimethylamino) ethyl methacrylate) (PDMAEMA) brushes with high density were synthesized on the surface of polystyrene latex by atom transfer radical polymerization (ATRP) using acetone/water as the solvent and CuCl/CuCl₂/bpy as the catalyst. It was found that the polydispersity of PDMAEMA brushes decreased with the increasing external CuCl₂ concentration. The polymer brushes showed their lower critical solution temperature (LCST) at 31 and 33 °C under pH values of 10.0 and 8.0, respectively. Dynamic light scattering studies demonstrate that PDMAEMA brushes were pH- and salt-responsive. PDMAEMA domains were used as the nanoreactors to generate gold nanoparticles on the surface of colloid particles. TEM results indicate that monodispersed gold nanoparticles were obtained. These gold composite nanoparticles displayed effective catalytic activity in the reduction of 4-nitrophenol by NaBH₄.     

pH and salt responsive poly(N,N-dimethylaminoethyl methacrylate) cylindrical brushes and their quaternized derivatives

We present the synthesis and characterization of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) cylindrical brushes, their pH responsiveness, and the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes. PDMAEMA brushes were prepared by atom transfer radical polymerization (ATRP) using the grafting-from strategy. Initiating efficiencies of the ATRP processes were determined by cleaving the side-chains and gel permeation chromatography (GPC) analysis. Due to the slow initiation and steric hindrance, the initiating efficiency is only around 50%. The PDMAEMA brushes show worm-like structures and pH responsiveness, as proven by dynamic light scattering (DLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Strong cationic polyelectrolyte PMETAI brushes were produced by quaternization of the PDMAEMA brushes. AFM and cryo-TEM images showed similar worm-like morphologies for the PMETAI brushes. The PMETAI brushes collapsed in solution with high concentration of monovalent salt, as proven by DLS and AFM results.     

Modification of carbon nanotubes with a nanothin polydopamine layer and polydimethylamino-ethyl methacrylate brushes

The work reports on a nondestructive pathway to produce polymer brush modified carbon nanotubes (CNTs) through surface-initiated polymerization followed by nanoparticle uploading. First, polydopamine layers with high surface coverage were formed on CNTs by spontaneous oxidative polymerization of dopamine. These were then used as the reactive layer for subsequent initiator attachment and brush grafting. Atom transfer radical polymerization of dimethylamino-ethyl methacrylate was initiated from the initiator layer, resulting in the formation of uniform polydimethylamino-ethyl methacrylate (PDMAEMA) brushes on the CNT surface. These were further quaternized by the reaction with CH₃I to form cationic Quaternized-PDMAEMA brushes (Q-PDMAEMA). The reversible solubilities of PDMAEMA- and Q-PDMAEMA-modified CNTs were achieved by switching between different solutions. Palladium nanoparticles were attached onto the CNTs using Q-PDMAEMA mediated anion exchange followed by in situ reduction using NaBH₄. The electrocatalytic behavior of the material was studied using an electrochemical method.     

Synthesis of binary mixed homopolymer brushes by combining atom transfer radical polymerization and nitroxide-mediated radical polymerization

This communication describes a novel strategy to synthesize binary mixed homopolymer brushes from mixed self-assembled monolayers (SAMs) on silica substrates by combining atom transfer radical polymerization (ATRP) and nitroxide-mediated radical polymerization (NMRP). Mixed SAMs terminated by ATRP and NMRP initiators were prepared by coadsorption of two corresponding organotrichlorosilanes from toluene solutions. Mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes were synthesized by ATRP of MMA at 80 °C followed by NMRP of styrene at 115 °C. Corresponding ‘free’ initiators were added into the solutions to control the polymerizations. We have found that the brush thickness increases with molecular weight in a nearly linear fashion. For a series of binary brushes consisting of PMMA of molecular weight of 26,200 and PS of various molecular weights, we have observed a transition in water contact angles with increasing PS molecular weight after CH₂Cl₂ treatment. Moreover, binary mixed polymer brushes with comparable molecular weights for two grafted polymers undergo reorganization in response to environmental changes, exhibiting different wettabilities.     

Growth of silver nanoparticles on poly(acrylic acid) brushes and their properties

A simple procedure is employed for the growth of silver nanoparticles (Ag NPs) onto the silicon substrate modified by poly(acrylic acid) (PAA) brushes, via: (1) surface-initiated ATRP of tert-butyl acrylate on Si surface to the preparation of poly(tert-butyl acrylate) brushes, (2) acid hydrolysis of PBA to the formation of PAA, and (3) in situ synthesis of Ag NPs via chemical reduction of AgNO₃ in the presence of PAA brushes. The polymer brushes are thoroughly characterized. Moreover, Ag nanoparticles are homogeneously immobilized into the brush layer and have been used to fabricate a sensor platform of surface-enhance Raman scattering for the detection of organic molecules and effectively catalyze the reduction of methylene blue by NaBH₄.     

Facile Incorporation of Silver Nanoparticles into Quaternized Poly(2‐(Dimethylamino)Ethyl Methacrylate) Brushes as Bifunctional Antibacterial Coatings

A simple strategy to fabricate bifunctional antibacterial coatings via in situ synthesis and incorporation of silver nanoparticles (AgNPs) into quaternized poly(2‐(dimethylamino)ethyl methacrylate) (qPDMAEMA) brushes without using any reducing agents is reported. PDMAEMA brushes are prepared on Si wafer substrates via surface‐initiated reverse atom transfer radical polymerization, which then are quaternized with ethyl bromide and hexyl bromide, respectively. The resulting qPDMAEMA‐AgNP nanocomposite coatings are characterized by using Fourier‐transform infrared spectroscopy (FT‐IR), X‐ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FE‐SEM), and Raman spectroscopy. FE‐SEM and Raman results indicate that the AgNPs with an average diameter of 35 nm are successfully loaded into the qPDMAEMA brushes. Furthermore, the antibacterial activities of the qPDMAEMA‐AgNP nanocomposite coatings against Gram‐positive Staphylococcus aureus and Gram‐negative Escherichia coli are investigated by both disc diffusion and colony‐forming unit methods. The results show excellent antibacterial properties of the nanocomposite coatings. The influence of the length of the quaternization agents on their antibacterial properties is also investigated.

     

Synthesis and responsive behavior of poly(N,N-dimethylaminoethyl methacrylate) brushes grafted on silica nanoparticles and their quaternized derivatives

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) was grafted onto the surface of silica nanoparticles via surface-initiated atom transfer radical polymerization to form temperature- and pH-responsive PDMAEMA brushes (silica-g-PDMAEMA). The resultant samples were characterized via ¹H NMR, transmission electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Their molecular weights and molecular weight distributions were determined by gel permeation chromatography analysis after silica content etching. The control of brush thickness and the responsive behavior were systematically investigated. Dynamic light scattering (DLS) results indicate that the brush thickness can be controlled by changing the polymerization time and the DMAEMA, initiator, and THF concentrations. According to DLS and zeta potential results, the lower critical solution temperature (LCST) of the PDMAEMA brushes shifts to a higher temperature with decreasing solution pH, which is attributed to the weak charge of the polyelectrolyte brushes. When the temperature is kept above the transition temperature, the silica-g-PDMAEMA nanoparticles aggregate into clusters and disaggregate during the cooling process. Moreover, with the heating/cooling step increasing, the aggregation and disaggregation temperatures are decreased. Meanwhile, when the molecular weight is increased from 13.6 × 10⁴ to 23.1 × 10⁴ g/mol, a decrease in the LCSTs at constant pH is observed. The related properties of the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes, were also discussed. The hydrodynamic radius of the silica-g-PMETAI nanoparticles decreases with increasing ionic strength, and a salting-out/salting-in effect is observed when the ionic strength is adjusted using NaI instead of NaCl.     

Effect of miscibility on migration of third component in star‐like co‐continuous and disperse‐within‐disperse mixed brushes

Novel ternary mixed‐brush single crystals were designed with disperse‐within‐disperse and star‐like co‐continuous morphologies based on poly(ethylene glycol) (PEG)‐b‐polystyrene (PS)/PEG‐b‐poly(methyl methacrylate) (PMMA)/PEG‐b‐polyaniline (PANI) and PEG‐b‐PS/PEG‐b‐PMMA/PEG‐b‐(poly(?‐caprolactone) (PCL) or poly(l ‐lactide) (PLLA)) block copolymers, respectively. In the disperse‐within‐disperse ternary mixed brushes, PANI nanorods were dispersed within the matrix (PS)–dispersed (PMMA) amorphous brushes. The flexibility and rigidity of brushes mainly affected the ultimate morphology and arrangement of amorphous coiled brushes in the vicinity of PANI nanorods. In addition, the migration of PCL and PLLA crystallizable brushes was evident into PMMA phases dispersed in the PS matrix, leading to star‐like co‐continuous patterns of PCL and PLLA brushes. This phenomenon was related to the miscibility of crystallizable PCL and PLLA brushes with the PMMA phase. The migration of crystallizable PCL and PLLA brushes increased the size of PMMA domains in the star‐like co‐continuous patterns. Despite the larger osmotic pressure of PLLA brushes, their higher miscibility with PMMA chains reflected the greater PMMA dispersal and wider PLLA star‐like branches. © 2017 Society of Chemical Industry     

Memory effect in polymer brushes containing pendant carbazole groups

Poly(9-(2-(4-vinyl(benzyloxy)ethyl)-9H-carbazole)) (PVBEC) brushes, have been successfully prepared on the silicon surfaces via surface-initiated atom transfer radical polymerization (ATRP). Conductance switching at a voltage of about −2.1 V is observed in the memory device based on the PVBEC brushes. The fabricated device shows the good memory characteristics as the ON/OFF current ratio up to 10⁵, and enduring 10⁶ read cycles under −1 V pulse voltages. Compared with those of the conventional Si/PVBEC/Al device fabricated by spin-coating, the switch voltage is lower and the ON/OFF current ratio is higher in the volatile Si-g-PVBEC/Al memory device.     

Optical tweezers to measure the interaction between poly(acrylic acid) brushes

Optical tweezers are employed to measure the forces of interaction within single pairs of poly(acrylic acid) (PAA) grafted colloids with an extraordinary resolution of ±0.5 pN. Parameters varied are the concentration and valency of the counterions (KCl, CaCl₂) of the surrounding medium as well as its pH. The data are quantitatively described by a recently published model of Jusufi et al. [Colloid Polym Sci 2004; 282:910] for spherical polyelectrolyte brushes which takes into account the entropic effect of the counterions. For the scaling of the brush height a power law is found having an exponent of 0.25 ± 0.02 which ranges between the values expected for spherical and planar brushes. From the model the ionic concentration inside the brush is estimated in reasonable agreement with the literature.     

Synthesis and characterization of TiO2 nanoparticles chemically coated with zwitterionic polymer brushes

This study introduces a synthetic method to graft zwitterionic poly (2-methacryroyloxyethyl phosphoryl choline) brushes onto TiO₂ nanoparticles with thickness of a few nanometers. The grafting of zwitterionic polymer brushes was characterized by electron microscope measurements, zeta-potential analysis, and thermo-gravimetric analysis. The technique we employed to synthesize those hybrid nanoparticles was a modified seeded emulsion polymerization in which the polymerization loci were changed in the stage of radical initiation and chain propagation. We have found that the polymerization loci should be on the surface for achieving the effective grafting of polymer brushes. From the suspension rheology studies, we have observed that the suspension of our hybrid nanoparticles was dominated by the attractive force as well as by packing volume effect. This unique rheological behavior is expected to be useful for understanding the inter-particle interactions in complex formulations.     

聚乙烯亚胺对Si3N4纳米微粒复合刷镀的影响

研究了聚乙烯亚胺对刷镀(Ni-P)-Si3N4纳米微粒复合镀液中Si3N4纳米微粒的分散性、刷镀层性能及结构的影响,并确定了聚乙烯亚胺在复合刷镀液中的最佳含量。结果表明,聚乙烯亚胺能有效阻止复合刷镀液中颗粒的絮凝、团聚,其用量对复合刷镀层中Si3N4含量、刷镀层硬度及耐磨性能有显著的影响。当其质量浓度为0.8 g/L时,获得了微粒均匀分散,稳定悬浮的复合刷镀液,复合刷镀层微观表面结构致密,微粒分布均匀,磨损量最小,显微硬度最大。     

Preparation of a hydrophobic cerium oxide nanoparticle coating with polymer binder via a facile solution route

In this work, cerium oxide (CeO₂) nanoparticles (NPs) were synthesized using a facile, low temperature solution process and coated using spin coating and spray coating approaches, for the fabrication of a hydrophobic surface coating. Silicon wafer (Si) substrates coated with CeO₂ NPs exhibited excellent hydrophobic behavior, but poor adhesion of the NPs to the substrate was observed - likely due to the low surface polarity of CeO₂ NPs. Polyacrylic acid (PAA) was introduced as an adhesion promoter to improve NP surface characteristics and obtain an adherent and cohesive coating. Slight polarity tuning and binder inclusion significantly enhanced the binding capability of the NPs as determined by peel-off measurements. The superior mechanical properties of NP coatings were attributed to the incorporation of PAA in the polymeric network. It improves inter-particle and particle-substrate secondary interactions, ultimately aiding NP cohesion and adhesion when deposited onto the Si substrate. The adhesive and hydrophobic properties of CeO₂ NP coatings were maintained upon exposure to high temperatures, and the coatings are transparent as well, making them suitable for various applications, such as cookware, glass coating and technology components.     

Architecture of colloidal crystals constructed by silica hybrid nanoparticles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter D_n = 192 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brushes encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization (ATRP) approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. We constructed the colloidal crystals using these photofunctional particles. Moreover, the SiO₂ particle array of colloidal crystals was locked by radical photopolymerization with vinyl monomer as a matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Controlled/Living Free Radical Polymerization of PS-b-P4-VP Brush Initiated from the Alkoxyamine-Functionalized Silicon Surface

Diblock copolymer brushes of polystyrene and poly (4-vinylpyridine) (PS-b-P4-VP) were synthesized by sequential monomers addition to a monolayer of 3-methacryloxypropyltrimeth-oxysilane. The diblock brushes were characterized by X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscope (AFM). The results suggested that the 3-methacryloxypropyltrimeth-oxysilane initiator layer grafted on the silicon surface and the PS-b-P4-VP chains were covalently anchored onto the Si/SiO₂/3-MPS surface.     

In situ-prepared composite materials of PEDOT: PSS buffer layer-metal nanoparticles and their application to organic solar cells

We report an enhancement in the efficiency of organic solar cells via the incorporation of gold (Au) or silver (Ag) nanoparticles (NPs) in the hole-transporting buffer layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which was formed on an indium tin oxide (ITO) surface by the spin-coating of PEDOT:PSS-Au or Ag NPs composite solution. The composite solution was synthesized by a simple in situ preparation method which involved the reduction of chloroauric acid (HAuCl₄) or silver nitrate (AgNO₃) with sodium borohydride (NaBH₄) solution in the presence of aqueous PEDOT:PSS media. The NPs were well dispersed in the PEDOT:PSS media and showed a characteristic absorption peak due to the surface plasmon resonance effect. Organic solar cells with the structure of ITO/PEDOT:PSS-Au, Ag NPs/poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM)/LiF/Al exhibited an 8% improvement in their power conversion efficiency mainly due to the enlarged surface roughness of the PEDOT:PSS, which lead to an improvement in the charge collection and ultimately improvements in the short-circuit current density and fill factor.     

Preparation of well-defined environmentally responsive polymer brushes on monolithic surface by two-step atom transfer radical polymerization method for HPLC

Well-defined poly (2-(dimethylamino) ethyl methacrylate) (PDMAEMA) brushes were successfully prepared on the monolithic surface via two-step atom transfer radical polymerization (ATRP). The polymer brushes synthesized by the second-step ATRP were based on the active bromic groups resulting from poly (ethylene glycol dimethacrylate) (pEDMA) monolith which was prepared at room temperature by the first-step ATRP. Element analysis was used to monitor the grafting process at different reaction times. Each step of preparation was characterized by scanning electron microscope, infrared spectrum and mercury intrusion porosimetry. Employment of PDMAEMA grafted monolith as the stationary phase for chromatographic analysis of steroids demonstrated that the PDMAEMA brushes possessed both pH- and salt-responsive properties. Noticeably, it has been found that the chain length of PDMAEMA brushes could influence the retention behavior of steroids due to the controllability of ATRP, which proposed an interesting alternative to modulate retention in HPLC. This is the first application of PDMAEMA brushes grafted monolith by two-step ATRP method for constructing responsive surface in HPLC and it might exploit a new path for widening the monolith application in various fields.     

Synthesis of polyethylene oxide end‐capped with perfluoroalkyl groups/polystyrene prototype brushes

Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free‐radical copolymerization of methacryloyl‐terminated PS and α‐vinylbenzyl‐ω‐hydroxy or α‐vinylbenzyl‐ω‐perfluoroalkyl (R_f) PEO macromonomers with the addition of Lewis acid (SnCl₄). It was found from their dilute‐solution properties that PS/PEO end‐capped with R_f (PBR_f), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,N‐dimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBR_f‐type brush by chemical modification, using corresponding acid chloride. The substitution of R_f groups was ～70% due to slipping of terminal hydroxy groups into PEO internal domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 772–778, 2006     

Architecture of prototype copolymer brushes composed of alternating structure and intramolecular phase separation of side chains in solution

Atom transfer radical polymerization (ATRP) was applied to the synthesis of prototype copolymer brushes composed polystyrene/poly(t‐butyl methacrylate) (PS/PBMA) alternating structure. Dilute solution properties of prototype copolymer brush were investigated by static and dynamic light scattering (SLS and DLS) in tetrahydrofuran (THF). As a result, such prototype copolymer brush composed of short aspect ratio formed a star‐like single molecule in THF. To discuss the intramolecular phase separation of PS/PBMA brushes in solution, we determined the radius of gyration (R_g) and cross‐sectional radius of gyration (R_g,c) of prototype copolymer brush by small‐angle X‐ray scattering (SAXS) using Guinier's plots in THF and styrene. We used styrene as solvent to cancel each other out with the electron density of PS side chains. Both R_g and R_g,c obtained in styrene decreased drastically compared with those obtained in THF. These results indicated strongly that PS and PBMA side chains of prototype brushes formed intramolecular phase separation even in good solvent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Arrays of size and distance controlled platinum nanoparticles fabricated by a colloidal method

Based on emulsion polymerization in the presence of a Pt complex, polystyrene (PS) particles were prepared exhibiting a well defined average diameter with narrow size-distribution. Furthermore, the colloids contain a controlled concentration of the Pt precursor complex. Optimized coating of Si substrates with such colloids leads to extended areas of hexagonally ordered close-packed PS particles. Subsequent application of plasma etching and annealing steps allows complete removal of the PS carriers and in parallel nucleation and growth of Pt nanoparticles (NPs) which are located at the original center of the PS colloids. In this way, hexagonally arranged spherical Pt NPs are obtained with controlled size and interparticle distances demonstrating variability and precision with so far unknown parameter scalability. This control is demonstrated by the fabrication of Pt NP arrays at a fixed particle distance of 185 nm while systematically varying the diameters between 8 and 15 nm. Further progress could be achieved by seeded emulsion polymerization. Here, Pt loaded PS colloids of 130 nm were used as seeds for a subsequent additional emulsion polymerization, systematically enlarging the diameter of the PS particles. Applying the plasma and annealing steps as above, in this way hexagonally ordered arrays of 9 nm Pt NPs could be obtained at distances up to 260 nm. To demonstrate their stability, such Pt particles were used as etching masks during reactive ion etching thereby transferring their hexagonal pattern into the Si substrate resulting in corresponding arrays of nanopillars.