Silver-filled polyethersulfone membranes for antibacterial applications — Effect of PVP and TAP addition on silver dispersion

Silver-filled asymmetric polyethersulfone (PES) membranes were prepared by a simple phase inversion technique. The effects of polyvinylpyrrolidone (PVP) and 2, 4, 6-triaminopyrimidine (TAP) on the surface properties of the silver-filled asymmetric membrane were investigated for antibacterial application. The dispersion of silver nanoparticles (Ag) and silver content on membrane surface were characterized using field emission scanning electron microscope (FESEM) and energy dispersive spectrometer (EDS), respectively. Results showed that smaller silver particles were formed in PES membranes when PVP and TAP were added during dope preparation. Using inductively coupled plasma mass spectrometry (ICP-MS), it is found that silver leaching has been significantly reduced up to 57% and 63% upon the addition of PVP and TAP respectively. The improved silver dispersion on membrane surfaces was able to enhance the antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) as evidenced by larger inhibition ring in agar diffusion method. The filtration of E. coli suspension (optical density = 0.31 at λ = 600 nm) carried out on prepared membranes proved that PES-AgNO₃ with TAP as dispersant appeared to inhibit almost 100% bacterial growth in rich medium. Hence, overall results showed the potential of PES-AgNO₃ with TAP to be used for antibacterial applications especially in water treatment.     

Preparation and antibacterial effects of PVA‐PVP hydrogels containing silver nanoparticles

The poly(vinyl alcohol)/poly(N‐vinyl pyrrolidone) (PVA–PVP) hydrogels containing silver nanoparticles were prepared by repeated freezing–thawing treatment. The silver content in the solid composition was in the range of 0.1–1.0 wt %, the silver particle size was from 20 to 100 nm, and the weight ratio of PVA to PVP was 70 : 30. The influence of silver nanoparticles on the properties of PVA–PVP matrix was investigated by differential scanning calorimeter, infrared spectroscopy and UV–vis spectroscopy, using PVA–PVP films containing silver particles as a model. The morphology of freeze‐dried PVA–PVP hydrogel matrix and dispersion of the silver nanoparticles in the matrix was examined by scanning electron microscopy. It was found that a three‐dimensional structure was formed during the process of freezing–thawing treatment and no serious aggregation of the silver nanoparticles occurred. Water absorption properties, release of silver ions from the hydrogels and the antibacterial effects of the hydrogels against Escherichia coli and Staphylococcus aureus were examined too. It was proved that the nanosilver‐containing hydrogels had an excellent antibacterial ability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 125–133, 2007     

Bioactivity and antibacterial activity against E-coli of calcium-phosphate-based glasses: Effect of silver content and crystallinity

In this work we developed improved bioactive glasses and glass-ceramics for biomedical applications, investigating their in vitro bioactivity, biocompatibility and antibacterial properties against E-Coli. A melt-quenched bioactive glass of the SiO₂-CaO-P₂O₅-MgO system was modified with the addition of 1 and 2 mol% Ag₂O and the 1 mol% Ag₂O-containing glasses were then heat treated to produce glass-ceramics. Surface modifications after soaking in SBF and ionic concentration changes showed that addition of silver and crystallization did not affect bioactivity although crystalline phases promoted a decrease in the degradation rate.Biocompatibility of all Ag-containing glasses and glass-ceramics was confirmed for certain samples concentrations. The antibacterial activity of the glasses against E-Coli was generally improved with decreasing particle size or increasing Ag₂O. The Ag-containing glass-ceramics with higher content of crystalline phase appears as a promising biocompatible biocidal material with potential applications in bone-related diseases.     

Chitosan/poly(dimethylaminoethylmethacrylate-co-hydroxyethylacrylate) based semi-IPN hydrogels and silver nanocomposites: Synthesis,evaluation of amoxicillin release studies,and antibacterial studies

To fabricate new smart materials that can deliver both the pharmaceutically active molecules and metal nanoparticles, we have formulated chitosan-based semi-IPN hydrogels and their silver nanocomposites (Ag NCs) along with amoxicillin (AMX). Semi-IPN hydrogels and their Ag NCs were synthesized from chitosan, dimethylamino ethyl methacrylate and 2-hydroxyethyl methacrylate via simple-free radical polymerization method and reducing with NaBH₄. The resultant formulations were evaluated for in vitro release of AMX, anti-bacterial studies and DNA cleavage studies. The hydrogels with AMX-derived silver nanoparticles (Ag NPs) show better ability to cleave DNA and anti-microbial activity than individual AMX and Ag NPs.     

Effect of silver loaded sodium zirconium phosphate (nanoAgZ) nanoparticles incorporation on PES membrane performance

Polyethersulfone (PES) based ultrafiltration membranes were fabricated via phase inversion by adding silver-loaded sodium zirconium phosphate nanoparticles (nanoAgZ) in PES casting solutions. The effect of nanoAgZ concentration on the membrane performance, i.e., morphology, hydrophilicity, thermal stability, permeation and antifouling properties was investigated. The results of thermal gravitational analysis (TGA) showed that the thermal stability of the hybrid membrane had been improved by the addition of nanoAgZ particles. Contact angle results indicated that the hydrophilicity of the modified membranes was enhanced. The contact angle of the membrane decreased from 71.5° to 52.6° with the increase of the nanoparticle content in the casting solution. Permeation experiment results showed that the modified PES membranes demonstrate better separation performance over the pure PES membrane. The pure water flux of PES membrane increased from 82.1 L/m² h to 100.6 L/m² h with the addition of the nanoparticles. Most importantly, the incorporation of the nanoAgZ particles enhanced the BSA fouling resistance and also the anti-biofouling performance of the membrane.     

Effect of annealing temperature on the morphology and antibacterial activity of Mg-doped zinc oxide nanorods

Herein, magnesium-doped zinc oxide nanorods (MgZnO NRs) were synthesized by the co-precipitation method and annealed at different temperatures in the range of 100–500?°C. The increase in the annealing temperature was found to influence both chemical and morphological structures of the MgZnO NRs: Ultraviolet–visible diffuse reflectance spectroscopy showed an increase in band gap with increase in the annealing temperature. Fourier-transform infrared spectra showed that two characteristic peaks at 487?cm^?1 and 442?cm^?1 corresponding to a weak Zn–O stretching initially decreased and then disappeared with increase in the annealing temperature. Moreover, the MgZnO NRs annealed at 100?°C had large crystallite size, high aspect ratio, and narrow edges. Remarkably, the MgZnO NRs annealed at 100?°C exhibited the highest antibacterial activity against both S. aureus and E. coli strains, attributed to the high aspect ratio and diffusion ability of the Zn²⁺ ions and large surface charge, crystallite size, and surface area. The MgZnO NRs annealed at the relatively low temperature of 100?°C could be easily produced commercially, in large quantities, and effectively used to prevent the growth of foodborne microbes in food packaging applications.     

Fouling of UF membrane by humic substance: Effects of molecular weight and powder-activated carbon (PAC) pre-treatment

Fouling characteristics of membranes with various molecular weight cut-offs (MWCO) were investigated. The effects of the molecular weights (MW) of humic acids and pre-treatment with PAC on membrane fouling were studied. It was found that the hydraulic resistance caused by fouling materials calculated using cake resistance in series model is a better indicator than the percentage of flux decline to assess the fouling of membranes with various MWCO. The effects of MWCO of membranes and MW of humic acids on membrane fouling can be explained by the different types of fouling mechanisms.     

The effects of molecular weight and polymorphism on the fracture and thermo-mechanical properties of a carbon-fibre composite modified by electrospun poly (vinylidene fluoride) membranes

The interlaminar toughening of a carbon-fibre reinforced composite by incorporation of electrospun polyvinylidene fluoride (PVDF) nanofibrous membranes was explored in this work. The electrospinning process of low and high molecular weight PVDF was optimised to form nanofibres free of defects with diameters averaging several hundred nanometres. The nanofibres were electrospun directly onto commercial pre-impregnated carbon fibre materials and under these optimised conditions, PVDF primarily crystallised in its β phase polymorphic form but significant variations were observed between samples. There is strong evidence from DMTA analysis to suggest that a partial miscibility between the amorphous phases of the PVDF nanofibres and the epoxy exists. The improved plastic deformation at the crack tip after inclusion of the nanofibres was directly translated to a 57% increase in the mode II interlaminar fracture toughness (in-plane shear failure). Conversely, the fracture toughness in mode I (opening failure) was slightly lower than the reference by approximately 20%, and the results were interpreted from the complex micromechanisms of failure arising from the changes in polymorphism and molecular weight of the PVDF.     

Development of electroless silver plating on Para‐aramid fibers and growth morphology of silver deposits

The development of a conductive fiber with flame resistance is an urgent concern particularly in national defense and other specialized fields. Aramid fibers (para‐ or meta‐) exihibit high strength and excellent fire resistance. Electroless silver plating on para‐aramid fibers and growth morphology of silver deposits was investigated in the present work. The surface of para‐aramid fibers was roughened using sodium hydride/dimethyl sulfoxide to guarantee successful electroless plating. Two complexing agents (ethylene diamine/ammonia) and two reducing agents (glucose/seignette salt) were used for the electroless silver plating bath design. Structure and properties of the resulting silver‐deposited para‐aramid fibers were evaluated based on scanning electron microscopy, silver weight gain percentage calculation, electrical resistance measurement, crystal structure analysis, and mechanical properties test. The results showed that a higher silver weight gain was advantageous to the improvement of conductivity for the silver‐deposited para‐aramid fibers. The obtained silver deposit was homogenous and compact. Electroless silver‐plating deposits were considered to be three‐dimensional nucleation and growth model (Volmer–Weber). Black, silver gray, and white deposits appeared sequentially with progressive plating. The breaking strength of silver‐deposited para‐aramid fibers remained at value up to 44 N. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The influence of membrane formation parameters on structural morphology and performance of PES/PDMS composite membrane for gas separation

In this study, influence of membrane preparation parameters on structural morphology and performance of polyethersulfone/polydimethylsiloxane (PES/PDMS) composite membrane was investigated for gas separation. Asymmetric PES flat sheet membranes were composed by phase inversion method and used as supports. PES composite membranes were fabricated by coating silicone rubber as selective layer on the top surface of support. Effects of different concentrations of PES and PDMS, solvent type, and support thickness on membrane performance were investigated for separation of oxygen from nitrogen. The optimized superior membrane was further modified using polyvinylidenfluoride, methanol and ethanol as additives in PES solutions and/or in water coagulation bath to promote the membrane capability. The results showed that addition of ethanol and methanol in cast solution and coagulation bath can greatly affect the morphology and hence the performance of the prepared membranes. The permeance changes have the contrary trend with solubility parameter difference between solvent and nonsolvent mixture, for instance when this parameter difference was lowest, higher permeance was obtained. Support and coating polymer concentration can control the permeance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyethersulfone/poly (butylene succinate) membrane: Effect of preparation conditions on properties and performance

In this study, biodegradable polymer of poly (butylene succinate) (PBS) was blended with polyethersulfone (PES) to prepare a novel semi-biodegradable membrane. The effect of blend ratio and coagulation bath temperature (CBT) was investigated on membrane characteristics including membrane morphology, mechanical strength and also treatment ability. Moreover, Fourier transform infrared (FTIR) spectrum, thermal stability, biodegradation and contact angle of the membranes were studied. Results demonstrated that the wastewater permeation through the prepared membranes was increased by blending the polymers and reached to maximum at blend ratio of 50/50. The wastewater treatment of PES/PBS blend membranes was improved by increasing PBS content.     

Preparation and characterization of hydrophilic and antibacterial silver decorated silica-grafted-poly(vinylpyrrolidone) (Ag-SiO2-PVP) nanoparticles for polymeric nanocomposites

Hydrophilic antibacterial silver decorated silica-grafted-poly(vinylpyrrolidone) (Ag-SiO₂-PVP) nanoparticles were successfully synthesized in multiple steps. In this regard, silanization of the silica nanoparticles was performed with different concentrations of vinyltrimethoxysilane (VTS) to generate vinyl groups onto the nanoparticles surface. Obtained results showed that by increasing the VTS concentration the amount of vinyl groups on the surface of the silica nanoparticles increased while nanoparticles agglomeration did not occur. Then, poly(vinylpyrrolidone) PVP brushes were grafted onto the silanized silica nanoparticles (SiO₂-VTS) via grafting-through polymerization method to obtain PVP-grafted silica nanoparticles (SiO₂-PVP). Fourier transform infrared spectroscopy, thermal gravimetric analysis, and dynamic light scattering confirmed the successful generation of the vinyl groups and PVP brushes onto the silica nanoparticles. Finally, Ag-SiO₂-PVP nanoparticles were prepared by synthesizing silver nanoparticles onto the SiO₂-PVP nanoparticles to render them antibacterial. Energy dispersive X-ray spectroscopy showed that highest grafting of silver nanoparticles onto the SiO₂-PVP nanoparticles was obtained for the nanoparticles with highest content of vinyl groups. X-ray photoelectron spectroscopy was used to identify the elements and their chemical structure for the synthesized nanoparticles. Plate colony counting method was applied to assess the antibacterial effects of the Ag-SiO₂-PVP nanoparticles which revealed outstanding bactericidal properties of them.     

Effect of silver nanoparticles on the electron transfer reactivity and the catalytic activity of myoglobin

Silver nanoparticles (11+/-1.5 nm) could greatly enhance the electron-transfer reactivity of myoglobin (Mb) and its catalytic ability toward hydrogen peroxide (H2O2). Direct fast electron transfer between Mb and a pyrolytic graphite (PG) electrode was achieved, and a pair of well-defined, quasi-reversible redox peaks was obtained. The cathodic and anodic peaks were located at -329 and -281 mV, respectively. Meanwhile, the catalytic ability of the protein toward the reduction of H2O2 was also studied, and a H2O2 biosensor was subsequently fabricated. Its detection limit was 1.0 x 10(-6) M with a sensitivity of 0.0205 microA per microM of H2O2. The apparent Michaelis-Menten constant was calculated to be 1303 muM. Flocculation assay showed that the protein maintained plasmon layers surrounding the surface of silver nanoparticles and avoided silver-nanoparticle aggregation. On the other hand, UV-visible spectroscopy studies revealed that silver nanoparticles could induce a small change of the heme-group environment of the protein; this contributed to the enhancement of the electron-transfer reactivity and the catalytic activity.     

On the enhanced antibacterial activity of plasma electrolytic oxidation (PEO) coatings that incorporate particles: A review

Biomaterials are substances of artificial or natural origin that are used to improve, treat, heal or replace the tissue or bone of a human or animal body. Due to the ever-increasing progress and the widespread use of biomaterials for various biomedical purposes, different methods are used to modify their surface characteristics. One of the problems facing biomaterials such as implants, prostheses, and stents is the presence of various bacteria that can cause adverse side effects such as infection, swelling, and tenderness. This raises the issue of their resistance to bacterial infection, a subject that needs to be thoroughly investigated. So far, a variety of methods have been developed to treat or coat biomaterials and make them resistant to bacterial infections. One of the most promising approaches is the plasma electrolytic oxidation (PEO) process. This process is not only successful in the formation of porous, hard, corrosion-resistant, wear-resistant, and biocompatible coatings but also can be easily manipulated to introduce antibacterial agents to the coatings structure. The addition of nano- or micro-sized particles in the electrolytes has been proven to not only modify the composition and structure of the PEO coatings, but also bring about a strong antibacterial activity. In light of recent advances in this field, the following review aims at discussing different aspects of particles addition in PEO electrolytes when the antibacterial activity is the main concern.     

An investigation of silver electrodeposition from ionic liquids: Influence of atmospheric water uptake on the silver electrodeposition mechanism and film morphology

The electrodeposition of silver from two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF₄]) and N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide ([C₄mPyr][TFSI]), and an aqueous KNO₃ solution on a glassy carbon electrode was undertaken. It was found by cyclic voltammetry that the electrodeposition of silver proceeds through nucleation–growth kinetics. Analysis of chronoamperometric data indicated that the nucleation–growth mechanism is instantaneous at all potentials in the case of [BMIm][BF₄] and [C₄mPyr][TFSI], and instantaneous at low overpotentials tending to progressive at high overpotentials for KNO₃. Significantly, under ambient conditions, the silver electrodeposition mechanism changes to progressive nucleation and growth in [C₄mPyr][TFSI], which is attributed to the uptake of atmospheric water in the IL. It was found that these differences in the growth mechanism impact significantly on the morphology of the resultant electrodeposit which is characterised ex situ by scanning electron microscopy and X-ray diffraction.     

Effect of polydimethylsiloxane macrodiol molecular weight on properties and morphology of polyurethane and polyurethaneurea

Two series of polyurethanes and polyurethaneureas were prepared using a two‐step bulk‐solution polymerization procedure. Each series consisted of three polymers based on three molecular weights of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS): 940, 1913, and 2955. The soft segment in all cases was an 80:20 mixture of PDMS and poly(hexamethylene oxide) (MW 700), and the hard segment was based on 4,4′‐methylenediphenyl diisocyanate and mixed chain extenders (40 wt %). In the polyurethane (PU) series the chain extender was a 60:40 (mol) mixture of BDO and 1,3‐bis(4‐hydroxybutyl)1,1,3,3‐tetramethyldisiloxane (BHTD), whereas in the polyurethaneurea (PUU) series it was a 60:40 (mol) mixture of BHTD and 1,2‐ethylenediamine. The polymerization was carried out by preparing a prepolymer using a bulk polymerization procedure followed by chain extension in a solution of N,N‐dimethylacetamide. Polymers were characterized by size‐exclusion chromatography, tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). The number‐average molecular weights of the polymers in the PU series were in the range of 114,300–124,500, whereas they were in the 78,400–103,300 range for the PUU series. Polymers with good clarity and mechanical properties were obtained with PDMS‐940 and PDMS‐1913, but those obtained from PDMS‐2955, despite having good tensile strength, had a low percentage of elongation, high modulus, and poor clarity. DSC and DMTA results indicated that regardless of the PDMS molecular weight, the siloxane segments existed as a highly phase‐separated state. This poor compatibility was consistent with the low solubility of PDMS compared to that of the hard‐segment‐forming components. The polymers in the polyurethane series exhibited multiple melting endotherms, attributed to the melting of ordered domains from different hard segments. The combined heats of fusion were similar for the materials in the PU series. In contrast, the polymers in the PUU series showed a hard‐segment order that was significantly less defined, with the heat of fusion approximately a third to a half that of the materials in the polyurethane series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1565–1573, 2003     

卤族元素对Ag电极电催化还原CO2的影响

通过在电解液中加入卤族元素,系统地研究了卤族元素对于CO的选择性和反应速率的影响。结果表明,卤族元素对于CO₂的还原反应具有促进作用,并按照Cl^- < Br^- < I^-的顺序递增。Cl^-和Br^-对CO₂还原反应和析氢反应都具有催化作用,而I^-的存在加快了CO的生成,对析氢反应没有明显影响。在过电势为590 mV时,CO在有I-溶液中的选择性是无I^-溶液的28倍。经过表征和分析后得出,I^-具有较强的吸附性能,通过化学吸附使催化剂表面形貌发生改变,CO的活性位增多,加快其反应速率。同时,I^-在反应过程中易向反应表面传输负电荷,增加与碳原子的相互作用,从而提高CO的生成速率。     

Effect of micron sized silver particles concentration on the adhesion induced by sintering and antibacterial properties of hydroxyapatite microcomposites

In this paper, silver microparticles were proposed as an additive (wetting agent) in the sintering of bovine bone-derived hydroxyapatite, and their well-known antibacterial properties were evaluated for the newly-developed materials. Hydroxyapatite was prepared by thermal processing of bovine bones, followed by milling and sorting. After silver addition, the samples were tested as precursors, green compacts and adhered particles-sintered compacts, using complementary morphological, compositional and structural evaluation techniques (scanning electron microscopy coupled with energy dispersive spectrometry, Fourier infrared spectroscopy, X-ray diffraction). The antibacterial effect was assessed on bacterial strains popular for their association with post-implantation infections. The study was designed to evaluate the precursors, investigate the surface, morphology and/or structure changes during forming and adhesion by sintering, and explore the relationship between the silver concentration and the antibacterial effect of the material. The results confirmed the benefits of adding silver as a wetting agent in sintering bovine bone-derived hydroxyapatite as well as its antibacterial effect (with best results at 2 wt%Ag). In spite of the great potential as a wetting agent and antibacterial factor in hydroxyapatite, the proper evaluation of these results requires extensive testing for elevating the control level in designing the material properties, and for establishing optimal concentrations of silver in order to achieve proper antibacterial and biocompatible behaviours.     

Effect of highly degraded high‐density polyethylene (HDPE) on processing and mechanical properties of wood flour‐HDPE composites

The influence of highly degraded high‐density polyethylene (HDPE) on physical, rheological, and mechanical properties of HDPE‐wood flour composites was studied. For this purpose, the virgin HDPE was subjected to accelerated weathering under controlled conditions for 200 and 400 h. The virgin and exposed HDPE and pine wood flour were compounded to produce wood flour‐HFPE composites. The results showed that the accelerated weathering highly degraded HDPE. Degradation created polar functional carbonyl groups and also produced extensive cross‐linking in HDPE and consequently poor processibility. The interruptions in the flow characteristics of the degraded HDPE potentially caused processing hurdles when using them for extrusion or injection molding manufacturing as only small part (10%) of virgin HDPE could be replaced by highly degraded HDPE for wood flour‐HDPE composite manufacturing. The mechanical properties of composites containing highly degraded HDPEs were similar to the composites with virgin HDPE and in some cases they exhibited superior properties, with the exception being with the impact strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013