Combination of electrografting and atom-transfer radical polymerization for making the stainless steel surface antibacterial and protein antiadhesive

A two-step "grafting from" method has been successfully carried out, which is based on the electrografting of polyacrylate chains containing an initiator for the atom transfer radical polymerization (ATRP) of 2-(tert-butylamino)ethyl methacrylate (TBAEMA) or copolymerization of TBAEMA with either monomethyl ether of poly(ethylene oxide) methacrylate (PEOMA) or acrylic acid (AA) or styrene. The chemisorption of this type of polymer brushes onto stainless steel surfaces has potential in orthopaedic surgery. These films have been characterized by ATR-FTIR, Raman spectroscopy, atomic force microscopy (AFM), and measurement of contact angles of water. The polymer formed in solution by ATRP and that one detached on purpose from the surface have been analyzed by size exclusion chromathography (SEC) and (1)H NMR spectroscopy. The strong adherence of the films onto stainless steel has been assessed by peeling tests. AFM analysis has shown that addition of hydrophilic comonomers to the grafted chains decreases the surface roughness. According to dynamic quartz crystal microbalance experiments, proteins (e.g., fibrinogen) are more effectively repelled whenever copolymer brushes contain neutral hydrophilic (PEOMA) co-units rather than negatively charged groups (PAA salt). Moreover, a 2- to 3-fold decrease in the fibrinogen adsorption is observed when TBAEMA is copolymerized with either PEOMA or AA rather than homopolymerized or copolymerized with styrene. Compared to the bare stainless steel surface, brushes of polyTBAEMA, poly(TBAEMA-co-PEOMA) and poly(TBAEMA-co-AA) decrease the bacteria adhesion by 3 to 4 orders of magnitude as revealed by Gram-positive bacteria S. aureus adhesion tests.     

Immobilization and Release Studies of Triazole Derivatives from Grafted Copolymer Based on Gellan-Carrying Betaine Units

New polymer-bioactive compound systems were obtained by immobilization of triazole derivatives onto grafted copolymers and grafted copolymers carrying betaine units based on gellan and N-vinylimidazole. For preparation of bioactive compound, two new types of heterocyclic thio-derivatives with different substituents were combined in a single molecule to increase the selectivity of the biological action. The 5-aryl-amino-1,3,4 thiadiazole and 5-mercapto-1,2,4-triazole derivatives, each containing 2-mercapto-benzoxazole nucleus, were prepared by an intramolecular cyclization of thiosemicarbazides-1,4 disubstituted in acidic and basic medium. The structures of the new bioactive compounds were confirmed by elemental and spectral analysis (FT-IR and ¹H-NMR). The antimicrobial activity of 1,3,4 thiadiazoles and 1,2,4 triazoles was tested on gram-positive and gram-negative bacteria. The triazole compound was chosen to be immobilized onto polymeric particles by adsorption. The Langmuir, Freundlich, and Dubinin–Radushkevich adsorption isotherm were used to describe the adsorption equilibrium. Also, the pseudo-first and pseudo-second models were used to elucidate the adsorption mechanism of triazole onto grafted copolymer based on N-vinylimidazole and gellan (PG copolymer) and grafted copolymers carrying betaine units (PGB1 copolymer). In vitro release studies have shown that the release mechanism of triazole from PG and PGB1 copolymers is characteristic of an anomalous transport mechanism.     

Thermoresponsive coatings strongly adhering to (semi)conducting surfaces

Thermoresponsive brushes have been efficiently grafted onto (semi)conductive surfaces by a two-step process. In the first step, poly(N-succinimidyl acrylate) chains have been chemisorbed onto silicon or stainless steel by the electrografting method. Then, these modified electrodes were immersed in isopropylamine in order to transform the grafted chains to the thermoresponsive poly(N-isopropyl acrylamide). The thermal response of these brushes has been shown by AFM. This straightforward grafting process is quite attractive for surface modification in confined media and is thus promising for microfludics application.     

Optimized grafting of antimicrobial peptides on stainless steel surface and biofilm resistance tests

Antibacterial peptides, magainin I and nisin were covalently bound to stainless steel surfaces. Several procedures of surface functionalisation processes have been investigated and optimized, each step being characterized by polarization modulation reflection absorption infrared spectroscopy (PM-RAIRS) and X-ray photoemission spectroscopy (XPS). Grafting of antibacterial peptides was successfully achieved by a 3 steps functionalisation process on a chitosan polymeric layer. The antibacterial activity of the anchored magainin and nisin was tested against a gram-positive bacteria, Listeria ivanovii, i.e., the possible survival and attachment of this bacteria, was characterized on modified stainless steel surfaces. The results revealed that the adsorbed peptides reduced the adhesion of bacteria on the functionalised stainless steel surface.     

Hydrolysis and grafting of dimethylalkoxysilanes onto stainless steel

The grafting of trialkoxysilane molecules should also give rise to the formation of a siloxane network at the substrate's surface when trialkoxysilanes are used. Other candidates that might be able to act as adhesion promoters at metallic surfaces are dimethylalkoxysilanes. The advantage of dimethylalkoxysilanes is that only one silanol group is produced during the hydrolysis step, leading to the formation of a grafted monolayer onto the steel. Moreover, the chemical grafting of stainless steel, which exhibits a low surface reactivity, is of great interest for industrial applications such as adhesive bonding or coatings. The objective of this work was to chemically graft dimethylalkoxysilanes onto AISI 316L stainless steel and to analyze the grafted layer by X‐ray photoelectron spectroscopy (XPS). Investigation of the hydrolysis of these molecules in aqueous solutions was also performed by proton nuclear magnetic resonance spectroscopy (¹H NMR). The grafting of 3‐(ethoxydimethylsilyl)propylamine (APDES) and 3‐glycidoxypropyldimethylethoxysilane (GPDES) was achieved onto stainless steel after a controlled hydrolysis reaction. A pH inferior or equal to 5 was necessary to obtain a sufficient hydrolysis of silanes. XPS results have evidenced the grafting of the silanes onto stainless steel. The signal of the Si 2p peak clearly showed the formation of a covalent bond between APDES and the stainless steel surface through the O atoms giving rise to a uniform layer of adsorbed molecules. Moreover, this grafted layer is strongly stable as no removal of the alkoxysilane was observed after immersion in hot water which is very critical for these molecules. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and Biological Activity of Acrylate Copolymers Containing 3-Oxo-N-allyl-1,2-benzisothiazole-3(2H)-carboxamide Monomer as a Marine Antifouling Coating

A type of grafted acrylate copolymer resins, containing 3-oxo-N-allyl-1,2-benzisothiazole-2(3H)-carboxamide monomer and heterocyclic monomers, was synthesized through the copolymeri- zation of methyl methacrylate (MMA) and butyl acrylate (BA) with functional monomers. The structures of the monomers and copolymers were validated by infrared (IR) and ¹H nuclear magnetic resonance (NMR) spectroscopies. The inhibitory activities of the copolymers on algae, bacteria, and barnacle larvae were measured, and the antifouling potencies against marine macrofouling organisms were investigated. The results showed that the grafted resin had significant inhibitory effects on the growth of three marine algae (Isochrysis galbana, Nannochloropsisoculata, and Chlorella pyrenoidosa), and three bacteria (Vibrio coralliilyticus, Staphylococcus aureus,and Vibrio parahaemolyticus). The target copolymers also showed excellent inhibition of the survival of barnacle larvae. Additionally, the release rate of the antifoulant and the results of the marine field tests indicated that the grafted copolymers had outstanding antifouling potency against the attachment of marine macrofouling organisms.     

Platelet and bacterial repellence on sulfonated poly(ethylene glycol)-acrylate copolymer surfaces

Novel poly(ethylene glycol) (PEG) and sulfonated PEG (PEG-SO₃) acrylate copolymers have been prepared and characterized to apply as coating and blending materials for biomedical applications. The modified surfaces using acrylate copolymers demonstrated increased hydrophilicity, possibly due to the hypothesized reorientation of PEG/PEG-SO₃ chains into water phase. All copolymer surfaces demonstrated less platelet adhesion than control. In addition, platelet adhesion on copolymer surfaces decreased as the chain length of PEG and sulfonated PEG in copolymers increases. All copolymer surfaces reduced bacterial adhesion significantly and the adhesion level differs depending on surfaces as well as media. The obtained results attest to the usefulness of these copolymers as a coating or additive material to improve the blood compatibility of blood contacting devices.     

High antibacterial efficiency of pDMAEMA modified silicon nanowire arrays

Materials of high antibacterial activity based on quaternized poly (2-(dimethylamino ethyl) methacrylate) (pDMAEMA) have been developed. DMAEMA was graft polymerized on silicon nanowire arrays (SiNWAs) by atom transfer radical polymerization (ATRP), and quaternized using benzyl chloride. The graft density on the modified nanowire arrays was much higher than on analogous smooth silicon, leading to higher bacterial adhesion on the nanowire arrays (34.6±0.39×10(6) vs. 5.0±0.15×10(6) cells/cm(2)). Incubation of Escherichia coli on the substrates for 18 h resulted in 95% cell death on the quaternized nanowire material compared to less than 45% on the quaternized smooth silicon. The results suggest that silicon nanowire array modified with quaternized pDMAEMA is a highly effective antibacterial material due to a high density of antibacterial polymer and consequent high bacterial adhesion and killing.     

Radiation-induced graft polymerization of acrylic acid onto fluorinated polymers. II. Graft copolymer–metal complexes obtained by radiation grafting onto poly(tetrafluoroethylene-ethylene) copolymer

A study has been made on the graft copolymers obtained by radiation-induced grafting of acrylic acid onto poly(tetrafluoroethylene-ethylene) (ET) films. The conversion of the graft copolymer into metal acrylate copolymer complex was carried out by treatment with different metal salts. Such a prepared graft copolymer–metal complex was confirmed by different methods: IR, UV spectrometry, degree of coloration, and x-ray fluorescence. Some selected properties of the graft copolymer–metal complexes such as electrical conductivity, swelling behavior, and mechanical properties were investigated. The influence of metal complexes in the graft copolymers was determined and compared with the grafted films. The possibility of the practical uses for such prepared graft copolymer–metal complexes was discussed and determined. It was assumed that such materials may be of great interest in the field of semiconducting materials in addition to their applicability as cation-exchange membranes. © 1993 John Wiley & Sons, Inc.     

Polymer Architectures via Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization

Various versatile chain transfer agents (CTAs) have been synthesized for reversible addition fragmentation chain transfer (RAFT) polymerzation. Such CTAs have been used to modify hydroxyl containing materials and produce well-controlled molecular architectures such as amphiphilic copolymer from poly (ethylene glycol), AB block copolymer consisting of a biodegradable segment, poly (l-lactic acid) (PLLA) and grafted copolymers of poly (styrene), poly (methyl methacrylate) and poly (methyl acrylate) from cellulose.     

Design of Well‐Defined Monofunctionalized Poly(3‐hexylthiophene)s: Toward the Synthesis of Semiconducting Graft Copolymers

The post‐functionalization of poly(3‐hexylthiophene) (P3HT) via various synthetic routes is reported. Well‐defined and monofunctionalized ω‐thiol‐terminated P3HT, ω‐carboxylic acid‐terminated P3HT, ω‐acrylate‐terminated P3HT, and ω‐methacrylate‐terminated P3HT are obtained in high yields through a straightforward procedure. From those, different novel P3HT‐based graft copolymers are synthesized following two routes: “grafting onto” and “grafting through” (macromonomer polymerization) methods. The synthesis of three types of graft copolymers is described. Each one has “rod” P3HT‐grafted side chains on a “coil” main chain, which can be polyisoprene, poly(vinyl alcohol), or poly(butyl acrylate). Each copolymer is characterized by size‐exclusion chromatography and NMR.     

Design of antibacterial surfaces by a combination of electrochemistry and controlled radical polymerization

In this paper we report a new method for the electrochemical deposition of a metal/polymer composite layer on a conducting substrate. The electrochemical solution is a mixture of an acrylate (ethyl acrylate, EA; 2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethyl acrylate, PTEA; 8-quinolinyl acrylate, 8QA), a metallic salt (silver(I) acetate), and a conducting salt in dimethylformamide. The process has been first studied with EA as the polymer precursor and then extended to PTEA and 8QA, respectively, with the purpose to prepare antibacterial surfaces. The final coating has been characterized by attenuated total reflection Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, environmental scanning electron microscopy, and atomic force microscopy. All the silver-containing coatings were effective against Gram-negative bacteria Escherichia coli. Bacteria Staphylococcus aureus could not adhere to the Ag(0)/polyacrylate films deposited on stainless steel.     

Tailoring of polymers by combination of ionic and radical controlled polymerizations

Poly(methyl methacrylate)s with terminal bromine atom, prepared by bromination of anionically polymerized MMA, were used as ATRP macroinitiators giving di- and triblock copolymers with MMA, styrene and butyl acrylate blocks. Multifunctional ATRP macroinitiators were synthesized by introducing bromomethyl or 2-bromoacyloxy groups onto the main chain of polystyrene or poly(4-methyl styrene) and used for ATRP grafting of tert-butyl acrylate leading to densely grafted copolymers with more or less uniform grafts.     

Antibacterial poly(D,L-lactide) (PDLLA) fibrous membranes modified with quaternary ammonium moieties

<正>Antibacterial poly(D,L-lactide)(PDLLA) fibrous membranes were developed via electrospinning,followed by surface modification which involved plasma pretreatment,UV-induced graft copolymerization of 4-vinylpyridine(4VP) and quaternization of the grafted pyridine groups with hexylbromide.The success of modification with quatemized pyridinium groups on the PDLLA fibrous membranes was ascertained by X-ray photoelectron spectroscopy(XPS).The antibacterial activities of these membranes were assessed against Gram-positive Staphylococcus aureus(S.aureus) and Gram-negative Escherichia coli(E.coli).The PDLLA fibrous membranes modified with quaternized pyridinium groups showed antibacterial efficiency against both bacteria as high as 99.999%.The results demonstrated that the antibacterial activity was based on the interaction of the positive charge of pyridinium group and negatively charged cell membrane of bacteria, resulting in loss of membrane permeability and cell leakage.     

Influence of alkyl chain length and molecular weight on the surface functionalization via adsorption/entrapment with biocidal cationic block copolymers

Polysulfone (PSf) films were functionalized with block copolymers containing poly(n-butyl acrylate) (PBA) as anchor block which is able to firmly tether the biocidal quaternized poly(2-dimethylaminoethyl methacrylate) (PDMAEMAq) to the surface. Block copolymers were synthesized using sequential atom transfer radical polymerization (ATRP) and quaternization with methyl and/or octyl groups rendered the polymers biocidal. Upon reversible swelling of the PSf surface layer in the adsorption/entrapment process, incorporation of the block copolymer is anticipated to be stable; homopolymers, i.e., methyl- or octyl-quaternized PDMAEMAq, were investigated for comparison. The addition of salt to the functionalization solution containing the block copolymer induced a decrease in the critical micelle concentration and lead to higher functionalization efficiency. The impact of intra- or interchain interactions in these aggregates on adsorption and firm entrapment in PSf was determined by measuring contact angle, charge density and zeta potential.     

Optimizing heavy-duty anticorrosive performances of coating films formed by acrylate-vinylidene chloride copolymer latexes through twice-painting technique

Twice-painting technique was adopted to prepare heavy-duty anticorrosive coating films formed by aqueous latexes of copolymers of vinylidene chloride(VDC) with an acrylate, namely methyl acrylate(MA), ethyl acrylate(EA), butyl acrylate(BA) or 2-ethylhexyl acrylate(EHA). Harsh salt-spray corrosion tests demonstrated that the optimized twicepainting technique was that the acidic latex solution was adjusted to p H 5-6 for the first painting, while it was utilized directly for the second painting. The test of 600 h of harsh salt-spray corrosion showed that MA-VDC85 coating could protect the steel excellently, whereas the other acrylate-VDC coatings with 75%-90% VDC content could not protect the steel so effectively. Further corrosion test showed that(1) MA-VDC85 coating protected steel from loss of metallic luster for at least 1000 h of salt-spray corrosion;(2) adhesion of MA-VDC85 coating to steel was excellent for at least 800 h of saltspray corrosion, but became very poor after 1000 h. Differential scanning calorimetry, thermogravimetric analysis, X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy were used to evaluate the corroded MA-VDC85 film.     

Antibacterial cotton fabric prepared by a “grafting to” strategy using a QAC copolymer

Quaternary ammonium compounds (QACs) have outstanding antimicrobial effect, but covalent immobilization of plentiful QAC onto cotton fiber surface to realize a durable function remains a challenge. Herein, a quaternary ammonium monomer, [2-(methacryloyloxy) ethyl] trimethylammonium chloride (DMC) was co-polymerized with methyl acrylate (MA) to prepare an antibacterial copolymer, poly(DMC-co-MA). To graft the copolymer with an improved grafting efficiency, cotton fabric was treated using carboxymethyl chitosan (CMC) to establish an amino-functionalized fiber surface first. This treatment allows the amidation reactions between the amino groups and the pendant ester groups in the poly(DMC-co-MA) to take place, achieving a durable anionic polymer coating onto the fiber surfaces with remarkably antibacterial effect. Characterization results indicated that when DMC/MA monomer ratio was 100:1, the resulting copolymer endows the modified cotton fabric with antibacterial capability that inactivates all Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Even after 50 laundering cycles, more than 98.0% of the antibacterial rate could still be retained. Moreover, the wearing comfort properties such as softness, water absorption and air permeability of the finishing cotton fabrics have been insignificantly changed by comparing to the untreated cotton fabric.

     

Antibacterial activities of polystyrene-block-poly(4-vinyl pyridine) and poly(styrene-random-4-vinyl pyridine)

Styrene was polymerized in the presence of benzoyl peroxide (BPO) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) to yield polystyrene-TEMPO (PS-TEMPO) macroinitiator. The PS-TEMPO macroinitiator with different molecular weight was reacted with 4-vinyl pyridine (4-VP) to synthesize polystyrene-block-poly(4-vinyl pyridine) (PS-b-PVP), which was then quaternized with n-octyl iodide. Antibacterial activity of the quaternized copolymers was assessed against a gram negative bacterium (Pseudomonas aeruginosa) and a gram positive one (Staphylococcus aureus) by using the shake flask test method, and the results were compared with those of poly(styrene-random-4-vinyl pyridine) (P(ST-r--VP)). The quaternized copolymers inhibited greatly the growth of the bacteria, and PS-b-PVP was more active than P(ST-r-VP), which was ascribed to the fact that the content of quaternized 4-VP units on the surface of the particles of the former copolymer was higher than that corresponding to the latter one.     

Graft copolymerization of methyl methacrylate onto curdlan

Graft copolymerization of methyl methacrylate onto curdlan was first investigated. In the graft copolymerization initiated by ammonium persulfate (APS) in DMSO under a homogeneous condition, the resulting graft copolymers had low molecular weights and low grafting percentages. However, the initiation by APS in water gave graft copolymers having relatively higher molecular weight ( ) and higher grafting percentage (548%) than those copolymers obtained by the homogeneous condition. When the graft copolymerization was carried out by cerium (IV) ammonium nitrate-HNO₃ initiation, the graft copolymer had the highest grafting percentage of 1620% without degradation of the curdlan backbone. The resulting graft copolymers were soluble in DMSO. The graft copolymers obtained by the cerium salt had narrow molecular weight distributions () compared with those by the APS catalyst in DMSO or water. The graft copolymers decomposed with sulfuric acid to isolate PMMAs, which molecular weights were larger than that of the corresponding homo-PMMAs. The structure of the grafted copolymers was characterized by IR, ¹³C NMR, DSC, and SEM. It was found that the graft copolymers exhibited the glass transition temperature (T_g), though curdlan had no T_g. As the grafting percentage increased, the T_g increased to reach 270°C, which was higher than the decomposition temperature of curdlan. The surface image of the grafted copolymers observed by SEM, showed smoothless compared with that of curdlan. It was also revealed that the graft copolymers having the grafting percentage of 1620% swelled in common organic solvents up to 4.5 times of the weight of the dry graft copolymer to form gels. © 1996 John Wiley & Sons, Inc.     

Responsive hybrid self-assemblies in aqueous media

Responsive copolymers have been prepared by grafting onto a poly(acrylamide-co-sodium acrylate) backbone [PAM-co-PANa] poly(N-isopropylacrylamide) stickers [PNIPA] characterized by a lower critical solution temperature (LCST) in water. From adsorption isotherms and DSC studies performed on PNIPA/silica mixtures, it was shown that PNIPA chains irreversibly interact with silica particles and that at low coverage they partially lose their responsiveness with temperature. When PNIPA is grafted onto a PAM-co-PANa backbone, which has no specific attraction to silica surfaces (only electrostatic repulsions), their binding process remains very similar to the one analyzed with PNIPA chains alone. Above critical copolymer and silica concentrations (Cp congruent with 1 g/L and CSi congruent with 30 g/L), hybrid networks can be formed following the rules of percolation theory. The viscoelastic properties of these networks are controlled by the concentration of inorganic cross links and the fraction of PNIPA grafts participating in bridges between particles, the others being involved in inelastic loops or pendant chains. For all of the mixtures investigated, an optimum weight ratio of RSi/PNIPA = 10-15 was found for the viscoelastic properties, in agreement with the saturation of silica beads by the copolymer. Because of the responsive behavior of PNIPA in aqueous solutions, graft copolymers are able to self-assemble with temperature, giving rise to a sol/gel transition upon heating. In the presence of added silica, hybrid aggregates (silica/PNIPA) coexist at high temperature with organic ones (PNIPA/PNIPA) with synergistic or antagonistic effects on the elastic properties depending on the proportion of PNIPA grafts per silica particle.