Surface Modification of Polyethylene Terephthalate Track-Etched Membranes by 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl Acrylate for Application in Water Desalination by Direct Contact Membrane Distillation.

In this work, the surfaces of poly (ethylene terephthalate) track-etched membranes (PET TeMs) with pore sizes of 670-1310 nm were hydrophobized with 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate (DFHA) by photoinitiated graft polymerization. Attenuated total reflection FTIR spectroscopy (ATR-FTIR), scanning electron microscopy (SEM) coupled to an energy-dispersive X-ray spectrometer (EDX), and contact angle measurements were used to identify and characterize the TeMs. The optimal parameters for graft polymerization were determined as follows: polymerization time of 60 min, monomer concentration of 30%, and distance from the UV source of 7 cm. The water contact angle of the modified membranes reached 97°, which is 51° for pristine membranes. The modified membranes were tested for water desalination using direct contact membrane distillation (DCMD) method. The effects of membrane pore size, the degree of grafting, and salt concentration on the performance of membrane distillation process were investigated. According to the results obtained, it has been concluded that large pore size hydrophobic TeMs modified by using DFHA could be used for desalinating water.

Preparation and application of stimuli-responsive PET TeMs: RAFT graft block copolymerisation of styrene and acrylic acid for the separation of water-oil emulsions.

Stimuli-responsive membranes play an important role in the fields of biomedicine, food and chemical industries, and environmental applications, including separation of water-oil emulsions. In this study, we present a method to fabricate pH-sensitive membranes using UV-initiated RAFT graft copolymerization of styrene (ST) and acrylic acid (AA) on poly(ethylene terephthalate) (PET) track-etched membranes (TeMs). The optimization of polymerization conditions led to successful grafting of polystyrene (PS) and poly(acrylic acid) (PAA) onto PET TeMs, resulting in membranes with stable hydrophobicity and pH change responsiveness. The membranes show a contact angle of 65° in basic environments (pH 9) and 97° in acidic environments (pH 2). The membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), thermogravimetric analyses (TGA), Fourier transform infrared spectroscopy (FTIR), contact angle (CA) methods. The PET TeMs-g-PS-g-PAA exhibited good performance in separating water-oil emulsions with a high efficiency of more than 90% and flux for direct chloroform-water 2500 L m-2 h-1 and reverse emulsions of benzene-water 1700 L m-2 h-1. This method of preparing stimuli-responsive membranes with controlled wettability and responsiveness to environmental pH provides versatility in their use in separating two types of emulsions: direct and reverse.

Effect of hydrophobized PET TeMs membrane pore-size on saline water treatment by direct contact membrane distillation.

This paper describes the desalination process by membrane distillation (MD) using track-etched membranes (TeMs). Hydrophobic track-etched membranes based on poly(ethylene terephthalate) (PET TeMs) with pore diameters from 700 to 1300 nm were prepared by UV-initiated graft polymerization of lauryl methacrylate (LMA) inside the nanochannels. Modified PET TeMs were investigated by Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and contact wetting angle (CA) measurements. Hydrophobic PET TeMs were tested for treating saline solutions of different concentrations by the direct contact membrane distillation (DCMD) method. The influence of membrane pore diameter and salt solution concentration on the water flux and rejection degree were investigated. Membranes with CA 94 ± 4° were tested in the direct contact membrane distillation (DCMD) of 7.5-30 g L-1 saline solution. Hydrophobic membranes with large pore sizes showed water fluxes in the range of 1.88 to 11.70 kg m-2 h-1 with salt rejection values of up to 91.4%.

Additive-free synthesis of poly(n-vinyl pyrrolidone) and poly(n-isopropylacrylamide) nanogels with controlled sizes.

An easy method is proposed to prepare poly(vinyl pyrrolidone) (PVP) and poly(N-isopropylacrylamide) (PNiPAAm) nanogels with sizes less than 100 nm. The underlying principle is to prepare dilute polymer solutions in acetone/water mixtures where acetone acts to break tridimensional structure of water hence disrupting the H-bonds bridging polymer coils causing separation and shrinkage in their sizes. Irradiation of these solutions by gamma-rays directly leads to the formation of intramolecular crosslinks within the coils resulting with nanogels with sizes smaller than precursor coils. While the average size of nanogels of PVP irradiated in water only is 236 nm, they were reduced to about 44 nm when irradiation was carried out in acetone/water solutions at near theta compositions. PNiPAAm nanogels were also synthesized by irradiating their dilute acetone/water solutions. Multimodal coil size distribution of PNiPAAm was converted into monomodal distribution with 70 nm average size and low dispersity by the addition of acetone. Irradiation of such solutions yielded PNiPAAm nanogels with 50 nm average size. Stability of nanogels was followed for 1 year not showing any changes in their sizes or size distributions. Nanogels were characterized by dynamic light scattering, scanning electron microscopy, and atomic force microscopy techniques.

Stimuli-Responsive Track-Etched Membranes for Separation of Water-Oil Emulsions.

In this work, we have developed a method for the preparation of pH-responsive track-etched membranes (TeMs) based on poly(ethylene terephthalate) (PET) with pore diameters of 2.0 ± 0.1 µm of cylindrical shape by RAFT block copolymerization of styrene (ST) and 4-vinylpyridine (4-VP) to be used in the separation of water-oil emulsions. The influence of the monomer concentration (1-4 vol%), the molar ratio of RAFT agent: initiator (1:2-1:100) and the grafting time (30-120 min) on the contact angle (CA) was studied. The optimal conditions for ST and 4-VP grafting were found. The obtained membranes showed pH-responsive properties: at pH 7-9, the membrane was hydrophobic with a CA of 95°; at pH 2, the CA decreased to 52°, which was due to the protonated grafted layer of poly-4-vinylpyridine (P4VP), which had an isoelectric point of pI = 3.2. The obtained membranes with controlled hydrophobic-hydrophilic properties were tested by separating the direct and reverse "oil-water" emulsions. The stability of the hydrophobic membrane was studied for 8 cycles. The degree of purification was in the range of 95-100%.

Folic acid-modified biocompatible Pullulan/poly(acrylic acid) nanogels for targeted delivery to MCF-7 cancer cells.

We prepared a novel nanogel consisting of poly(acrylic acid) (PAA) and pullulan (Pull) via a facile and green irradiation protocol. Synthesized nanogels were modified with bovine serum albumin (BSA) and folic acid (FA) and then loaded with doxorubicin (DOX) to obtain a delivery system with tumor-specific targeting ability and enhanced biocompatibility. In-vitro DOX release was investigated at different pH values, and it was found that DOX release was higher in acidic media, which is an advantage for the internalization of nanoparticles in acidic tumor environment. MTT assay and DAPI staining were performed to evaluate the effects of nanogels on L929 and MCF-7 cells. Based on the results of in vitro studies, DOX-loaded nanogels were found to be effective on cancer cells, while the neat ones were nondestructive in both lines. Overall, we envision that the biocompatible and tumor-specific nanogels could be a promising safe drug carrier system for cancer therapy.

Graft Polymerization of Stearyl Methacrylate on PET Track-Etched Membranes for Oil-Water Separation.

In this article, results of PET track-etched membranes (PET TeMs) hydrophobized by photo-induced graft polymerization of stearyl methacrylate (SM) inside the pores were presented. The effects of monomer concentration, time of irradiation and the nature of the solvent on the degree of grafting and membrane morphology were investigated. The PET TeMs with pore diameters ranging from 350 nm (pore density of 1 × 108 pore/cm2) to 3.05 µm (pore density of 1 × 106 pore/cm2) were hydrophobized and tested for oil-water separation by using hexadecane-water and chloroform-water emulsions. Studies have shown high separation performance for membranes (up to 1100 mL/m2·s) with large pore diameters while achieving a high degree of purification.

Radiolytic degradation of carbaryl in aqueous solution by gamma-irradiation/H2O2 process.

In this study the synergetic effect of gamma-ray and hydrogen peroxide on the degradation of carbaryl in aqueous solution were investigated. Aqueous solution of carbaryl was exposed to five different irradiation doses in the presence and absence of hydrogen peroxide. The intermediate species and aliphatic acids formed during irradiation were determined by Gas chromatography-Mass spectrometer and Ion Chromatography, respectively. It was found that the gamma-irradiation accelerate the degradation process of carbaryl with and without hydrogen peroxide. The inconstancy in pH, dissolved oxygen and total acidity was evaluated before and after treatment by gamma. It was found that the pH was decline from 6.71 to 5, dissolved oxygen from 2.64 to 0.9 mgL-1 and the total acidity was raised from 0.44 to 0.61 mgL-1. The entirely degradation of Carbaryl takes place at 3.0 kGy and 9.6 mM hydrogen peroxide, H2O2. As a consequence, the possible degradation pathway was suggested.

Green and Facile Synthesis of Pullulan-Stabilized Silver and Gold Nanoparticles for the Inhibition of Quorum Sensing.

Pullulan (Pull) decorated with monodisperse Ag and Au nanoparticles (NPs) was synthesized by a simple and green method. Samples were characterized by FTIR, UV-vis, NMR, XRD, TGA, SEM, XPS, DLS, and TEM. SEM images showed highly oriented microforms reported for the first time for Pull, because of the supramolecular self-assembling behavior of Pull chains. Antimicrobial and quorum sensing (QS) inhibition activities were tested against six pathogen bacteria and reporter and biomonitor strain. Pull decorated with NPs, in particular, Ag-modified ones, outperformed pristine Pull. The cell proliferation was tested with an MTT assay. NPs-decorated Pull was studied for the first time as an inhibitory agent against bacterial signal molecules and found to be a good candidate. The promising performance of AgNPs@Pull compared to the commercial antibiotic gentamicin showed that it has great potential as a therapeutic approach to overcome the bacterial resistance that has developed against conventional antibiotics.

Recent Progress in the Membrane Distillation and Impact of Track-Etched Membranes.

Membrane distillation (MD) is a rapidly developing field of research and finds applications in desalination of water, purification from nonvolatile substances, and concentration of various solutions. This review presents data from recent studies on the MD process, MD configuration, the type of membranes and membrane hydrophobization. Particular importance has been placed on the methods of hydrophobization and the use of track-etched membranes (TeMs) in the MD process. Hydrophobic TeMs based on poly(ethylene terephthalate) (PET), poly(vinylidene fluoride) (PVDF) and polycarbonate (PC) have been applied in the purification of water from salts and pesticides, as well as in the concentration of low-level liquid radioactive waste (LLLRW). Such membranes are characterized by a narrow pore size distribution, precise values of the number of pores per unit area and narrow thickness. These properties of membranes allow them to be used for more accurate water purification and as model membranes used to test theoretical models (for instance LEP prediction).

Modification of PET Ion-Track Membranes by Silica Nanoparticles for Direct Contact Membrane Distillation of Salt Solutions.

The paper describes desalination by membrane distillation (MD) using ion-track membranes. Poly(ethylene terephthalate) (PET) ion-track membranes were hydrophobized by the immobilization of hydrophobic vinyl-silica nanoparticles (Si NPs). Si NPs were synthesized by the sol-gel method, and the addition of the surfactant led to the formation of NPs with average size of 40 nm. The thermal initiator fixed to the surface of membranes allowed attachment of triethoxyvinyl silane Si NPs at the membrane surface. To further increase hydrophobicity, ethoxy groups were fluorinated. The morphology and chemical structure of prepared membranes were characterized by SEM, FTIR, XPS spectroscopy, and a gas permeability test. Hydrophobic properties were evaluated by contact angle (CA) and liquid entry pressure (LEP) measurements. Membranes with CA 125-143° were tested in direct contact membrane distillation (DCMD) of 30 g/L saline solution. Membranes showed water fluxes from 2.2 to 15.4 kg/(m2·h) with salt rejection values of 93-99%.

Cu/CuO Composite Track-Etched Membranes for Catalytic Decomposition of Nitrophenols and Removal of As(III).

One of the promising applications of nanomaterials is to use them as catalysts and sorbents to remove toxic pollutants such as nitroaromatic compounds and heavy metal ions for environmental protection. This work reports the synthesis of Cu/CuO-deposited composite track-etched membranes through low-temperature annealing and their application in catalysis and sorption. The synthesized Cu/CuO/poly(ethylene terephthalate) (PET) composites presented efficient catalytic activity with high conversion yield in the reduction of nitro aryl compounds to their corresponding amino derivatives. It has been found that increasing the time of annealing raises the ratio of the copper(II) oxide (CuO) tenorite phase in the structure, which leads to a significant increase in the catalytic activity of the composites. The samples presented maximum catalytic activity after 5 h of annealing, where the ratio of CuO phase and the degree of crystallinity were 64.3% and 62.7%, respectively. The catalytic activity of pristine and annealed composites was tested in the reduction of 4-nitroaniline and was shown to remain practically unchanged for five consecutive test cycles. Composites annealed at 140 °C were also tested for their capacity to absorb arsenic(III) ions in cross-flow mode. It was observed that the sorption capacity of composite membranes increased by 48.7% compared to the pristine sample and reached its maximum after 10 h of annealing, then gradually decreased by 24% with further annealing.

Application of radiation for the synthesis of poly(n-vinyl pyrrolidone) nanogels with controlled sizes from aqueous solutions.

Controlling of sizes of nanogels is very important for any biomedical application. In the present study we report a facile and reproducible method of preparing biocompatible nanogels of poly(N-vinyl pyrrolidone) (PVP) which were synthesized by using either electron beam (e-beam) (NGEB) or gamma irradiation (NGG) of dilute aqueous solutions. Nanogels with different hydrodynamic sizes were obtained at the variance of the polymer molecular weight, concentration, type of radiation source hence dose rate and total absorbed dose. For the first time a comparative study of gamma and e-beam irradiation was made on the same polymer with the aim of controlling sizes of nanogels in the range of 30-250 nm. Moreover the stability of radiation-synthesized nanogels was followed up to 2 years in refrigerated solution and found to retain their original sizes and distributions enabling their long-term storage and use. The synthesized nanogels were characterized by using dynamic light scattering (DLS), gel permeation chromatography (GPC), scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. This work provides a clue to the fundamental question of how to control sizes of nanogels without using any additives which are indispensable with the other techniques. The technique is applicable to any water soluble polymer.

Detailed positron annihilation lifetime spectroscopic investigation of atrazine imprinted polymers grafted onto PE/PP non-woven fabrics.

This study presents the preparation of molecularly imprinted matrices by using radiation-induced grafting technique onto polyethylene/polypropylene (PE/PP) non-woven fabrics. Atrazine imprinted polymers were grafted onto PE/PP non-woven fabrics through the use of methacrylic acid (MAA) and ethylene glycol dimethylacrylate (EGDMA) as the functional monomer and crosslinking agent, respectively. Grafted MIPs were characterized by attenuated total reflectance Fourier transform infra-red spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), elemental analysis, scanning electron microscopy (SEM), and positron annihilation lifetime spectroscopy (PALS). The average diameter of free volume holes was determined as 0.612 nm which correlates very well with the size of template molecule atrazine, 0.512 nm. Binding behaviors were investigated against various factors, such as concentration of template molecule, pH, and contact time. Furthermore, the specific selectivity of grafted MIP on non-woven fabric was studied by using other common triazine compounds, such as simazine and metribuzine which show structural similarities to atrazine. The specific binding values for atrazine, simazine, and metribuzine were determined as 40%, 2.5%, and 1.5%, respectively.

Mineralization of paracetamol in aqueous solution with advanced oxidation processes.

Paracetamol is a common analgesic drug widely used in all regions of the world more than hundred tonnes per year and it poses a great problem for the aquatic environment. Its phenolic intermediates are classified as persistent organic pollutants and toxic for the environment as well as human beings. In the present study, the irradiation of aqueous solutions of paracetamol with 60Co gamma-rays was examined on a laboratory scale and its degradation path was suggested with detected radiolysis products. The synergic effect of ozone on gamma-irradiation was investigated by preliminary ozonation before irradiation which reduced the irradiation dose from 5 to 3 kGy to completely remove paracetamol and its toxic intermediate hydroquinone from 6 to 4 kGy as well as increasing the radiation chemical yield (Gi values 1.36 and 1.66 in the absence and presence of ozone, respectively). The observed amount of formed hydroquinone was also decreased in the presence of ozone. There is a decrease in pH from 6.4 to 5.2 and dissolved oxygen consumed, which is up to 0.8 mg l(-1), to form some peroxyl radicals used for oxidation. Analytical measurements were carried out with gas chromatography/mass spectrometry and ion chromatography (IC) both qualitatively and quantitatively. Amounts of paracetamol and hydroquinone were measured with gas chromatography after trimethylsilane derivatization. Small aliphatic acids, such as acetic acid, formic acid and oxalic acid, were measured quantitatively with IC as well as inorganic ions (nitrite and nitrate) in which their yields increase with irradiation.

The effect of environmental humidity on radiation-induced degradation of carrageenans.

Better understanding of the chemistry of radiation-induced degradation is becoming of increasing importance on account of the utilization of polymeric materials in a variety of radiation environments as well as beneficial uses of degraded polymers. In this report the importance of environmental humidity on the degrading effect of radiation has been considered from the point of view of controlling the molecular weights of kappa- and iota-carrageenans. These two polysaccharides were irradiated in solid form under strictly controlled environmental humidity conditions by incubating and later irradiating the samples over saturated aqueous salt solutions of NaCl, NaNO3 and MgCl2. The degradation was followed in detail by a careful gel permeation chromatographic analysis of their respective molecular weights before and after irradiation. The chain scission yield values G(S) were found to decrease with the water adsorbed from environment at every absorbed dose in the range of 5-100 kGy. On the other hand at very high water uptakes the yield of chain scission again increases especially at low doses. The decrease in degradation yield was attributed to the plastifying effect of water trapped in between the polymer chains facilitating the macroradical recombinations thus reducing the extent of chain scission. This study showed that although carrageenans were irradiated in solid form, the difference in their water uptake from changing environmental humidity has a profound effect in controlling their molecular weights by irradiation with ionizing radiation.

Development and evaluation of paclitaxel nanoparticles using a quality-by-design approach.

The aims of this study were to develop and characterize paclitaxel nanoparticles, to identify and control critical sources of variability in the process, and to understand the impact of formulation and process parameters on the critical quality attributes (CQAs) using a quality-by-design (QbD) approach. For this, a risk assessment study was performed with various formulation and process parameters to determine their impact on CQAs of nanoparticles, which were determined to be average particle size, zeta potential, and encapsulation efficiency. Potential risk factors were identified using an Ishikawa diagram and screened by Plackett-Burman design and finally nanoparticles were optimized using Box-Behnken design. The optimized formulation was further characterized by Fourier transform infrared spectroscopy, X-ray diffractometry, differential scanning calorimetry, scanning electron microscopy, atomic force microscopy, and gas chromatography. It was observed that paclitaxel transformed from crystalline state to amorphous state while totally encapsulating into the nanoparticles. The nanoparticles were spherical, smooth, and homogenous with no dichloromethane residue. In vitro cytotoxicity test showed that the developed nanoparticles are more efficient than free paclitaxel in terms of antitumor activity (more than 25%). In conclusion, this study demonstrated that understanding formulation and process parameters with the philosophy of QbD is useful for the optimization of complex drug delivery systems.

Analytical and toxicological studies of decomposition of insecticide parathion after gamma-irradiation and ozonation.

The decomposition of the widely used organophosphorus pesticide parathion was carried out in aqueous solutions by the use of gamma-irradiation from a 60Co source or ozonation by means of an ozone generator, and by combined processes of ozonation and radiolysis. Factors affecting the parathion decomposition as well formation and decomposition of the main by-products, including irradiation dose, length of ozonation time, and presence of common scavengers, were investigated. The most efficient was found to be the gamma-irradiation process combined with a short ozonation period; about 1 kGy irradiation dose was sufficient to decompose the pesticide in 15 mg/L solutions. Chemical studies of the decomposition of parathion were accompanied by monitoring of toxicity changes of irradiated solutions with the Microtox test.

Microplates with adaptive surfaces.

Here we present a new and versatile method for the modification of the well surfaces of polystyrene microtiter plates (microplates) with poly(N-phenylethylene diamine methacrylamide), (poly-NPEDMA). The chemical grafting of poly-NPEDMA to the surface of microplates resulted in the formation of thin layers of a polyaniline derivative bearing pendant methacrylamide double bonds. These were used as the attachment point for various functional polymers through photochemical grafting of various, for example, acrylate and methacrylate, polymers with different functionalities. In a model experiment, we have modified poly-NPEDMA-coated microplates with a small library of polymers containing different functional groups using a two-step approach. In the first step, double bonds were activated by UV irradiation in the presence of N,N-diethyldithiocarbamic acid benzyl ester (iniferter). This enabled grafting of the polymer library in the second step by UV irradiation of solutions of the corresponding monomers in the microplate wells. The uniformity of coatings was confirmed spectrophotometrically, by microscopic imaging and by contact angle measurements (CA). The feasibility of the current technology has been shown by the generation of a small library of polymers grafted to the microplate well surfaces and screening of their affinity to small molecules, such as atrazine, a trio of organic dyes, and a model protein, bovine serum albumin (BSA). The stability of the polymers, reproducibility of measurement, ease of preparation, and cost-effectiveness make this approach suitable for applications in high-throughput screening in the area of materials research.

Dynamic swelling behavior of gamma-radiation induced polyelectrolyte poly(AAm-co-CA) hydrogels in urea solutions.

The aim of this study was to investigate the equilibrium swelling properties in urea solutions of gamma-radiation induced polyelectrolyte copolymeric hydrogels consisting of acrylamide (AAm) and crotonic acid (CA). Poly(acrylamide-co-crotonic acid), poly(AAm-co-CA) hydrogels containing different amounts of CA were obtained in the form of rods after radiation. Swelling experiments were performed in aqueous urea solutions at 25 degrees C, gravimetrically. The hydrogels showed large extents of swelling in aqueous (urea/water) media the swelling being highly dependent on the chemical composition of the hydrogels and irradiation dose. The percentage swelling of poly(AAm-co-CA) hydrogels was between 1160 and 4250%, while that of the AAm hydrogels was between 670 and 900%. The diffusional exponent values (n) are between 0.51 and 0.66, hence the diffusion of urea/water into the hydrogels is non-Fickian. Equilibrium urea/water contents of the hydrogel systems were changed between 0.870 and 0.977.