Dendrimer-functionalized electrospun nanofibres as dual-action water treatment membranes.

This work reports the preparation of composite electrospun membranes combining antimicrobial action with the capacity of retaining low-molecular weight non-polar pollutants. The membranes were electrospun blends of polyvinyl alcohol (PVA) and poly(acrylic acid) (PAA) stabilized using heat curing. The membranes were functionalized by grafting amino-terminated poly(amidoamine) (PAMAM) G3 dendrimers. The antimicrobial effect was assessed using strains of Escherichia coli and Staphylococcus aureus by tracking their capacity to form new colonies and their metabolic impairment upon contact with membranes. The antimicrobial activity was particularly high to the gram-positive bacterium S. aureus with a 3-log reduction in their capacity to colonize dendrimer-functionalized membranes with respect to neat PVA/PAA fibers. The effect to gram-positive bacteria was attributed to the interaction of dendrimers with the negatively charged bacterial membranes and resulted in membranes essentially free of bacterial colonization after 20h in contact with cultures at 36°C. The adsorption of toluene on PAA/PVA fibers and on dendrimer-functionalized membranes was assayed using toluene over a broad concentration range. The host-guest encapsulation of toluene inside dendrimer molecules was computed through docking studies, which allowed calculating a maximum capacity of 14 molecules of toluene per molecule of PAMAM G3. The theoretical prediction was in good agreement with the experimental capacity at the higher concentrations assayed.

Antimicrobial activity of poly(vinyl alcohol)-poly(acrylic acid) electrospun nanofibers.

Electrospun nanofibers were prepared from blends of poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA). The fibers were stabilized by heat curing at 140°C via anhydride and ketone formation and crosslinking esterification. The antimicrobial effect was assessed using strains of Escherichia coli and Staphylococcus aureus by tracking their capacity to form colonies and their metabolic impairment upon contact with PAA/PVA membranes. Membranes containing >35wt.% PAA displayed significant antibacterial activity, which was particularly high for the gram-positive S. aureus. All membranes were negatively charged, with surface ζ-potential in the (-34.5)-(-45.6)mV range, but the electrostatic interaction with the negatively charged cells was not the reason for the antimicrobial effect. Neither pH reduction nor the passing of non-crosslinked polymers to the solution affected microbial growth. The antibacterial activity was attributed to the chelation of the divalent cations stabilizing the outer cell membrane. The effect on gram-positive bacteria was attributed to the destabilization of the peptidoglycan layer. The sequestration of divalent cations was demonstrated with experiments in which calcium and a chelating agent were added to the cultures in contact with membranes. The damage to bacterial cells was tracked by measuring their surface charge and the evolution of intracellular calcium during the early stages after contact with PAA/PVA membranes.

Fate and transformation products of amine-terminated PAMAM dendrimers under ozonation and irradiation.

This article deals with the degradation of a third-generation (G3) poly(amidoamine) (PAMAM) dendrimer under ozonation and irradiation. The identification and quantification of G3 PAMAM dendrimer and its transformation products has been performed by liquid chromatography-electrospray ionization-hybrid quadrupole time-of-flight-mass spectrometry. The dendrimer was completely depleted by ozone in less than 1 min. The effect of ultraviolet irradiation was attributed to hydroxyl-mediated oxidation. The transformation products were attributed to the oxidation of amines, which resulted in highly oxidized structures with abundance of carboxylic acids, which started from the formation of amine oxide and the scission of the CN bond of the amide group. We studied the toxicity of treated mixtures for six different organisms: the acute toxicity for the bacterium Vibrio fischeri and the microcrustacean Daphnia magna, the multigenerational growth inhibition of the alga Pseudokirchneriella subcapitata, and the seed germination phytotoxicity of Licopersicon esculentum, Lactuca sativa and Lolium perenne. Ozonation and irradiation originated transformation products are more toxic than the parent dendrimer. The toxicity of the dendrimer for the green alga was linked to a strong increase of intracellular reactive oxygen species with intense lipid peroxidation.

Energy efficiency for the removal of non-polar pollutants during ultraviolet irradiation, visible light photocatalysis and ozonation of a wastewater effluent.

This study aims to assess the removal of a set of non-polar pollutants in biologically treated wastewater using ozonation, ultraviolet (UV 254 nm low pressure mercury lamp) and visible light (Xe-arc lamp) irradiation as well as visible light photocatalysis using Ce-doped TiO2. The compounds tracked include UV filters, synthetic musks, herbicides, insecticides, antiseptics and polyaromatic hydrocarbons. Raw wastewater and treated samples were analyzed using stir-bar sorptive extraction coupled with comprehensive two-dimensional gas chromatography (SBSE-CG × GC-TOF-MS). Ozone treatment could remove most pollutants with a global efficiency of over 95% for 209 µM ozone dosage. UV irradiation reduced the total concentration of the sixteen pollutants tested by an average of 63% with high removal of the sunscreen 2-ethylhexyl trans-4-methoxycinnamate (EHMC), the synthetic musk 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (tonalide, AHTN) and several herbicides. Visible light Ce-TiO2 photocatalysis reached ~70% overall removal with particularly high efficiency for synthetic musks. In terms of power usage efficiency expressed as nmol kJ(-1), the results showed that ozonation was by far the most efficient process, ten-fold over Xe/Ce-TiO2 visible light photocatalysis, the latter being in turn considerably more efficient than UV irradiation. In all cases the efficiency decreased along the treatments due to the lower reaction rate at lower pollutant concentration. The use of photocatalysis greatly improved the efficiency of visible light irradiation. The collector area per order decreased from 9.14 ± 5.11 m(2) m(-3) order(-1) for visible light irradiation to 0.16 ± 0.03 m(2) m(-3) order(-1) for Ce-TiO2 photocatalysis. The toxicity of treated wastewater was assessed using the green alga Pseudokirchneriella subcapitata. Ozonation reduced the toxicity of treated wastewater, while UV irradiation and visible light photocatalysis limited by 20-25% the algal growth due to the accumulation of reaction by-products. Three transformation products were identified and tracked along the treatments.

An insight into the mechanisms of nanoceria toxicity in aquatic photosynthetic organisms.

The effect of nanoceria on two aquatic photosynthetic organisms of ecological relevance, a green alga and a cyanobacterium, is reported. The main bioenergetic process of these organisms, photosynthesis, was studied by measuring both oxygen evolution and chlorophyll a fluorescence emission parameters. Nanoceria significantly inhibited photosynthesis in the cyanobacterium in the entire range of concentrations tested (0.01-100 mg/L), while a dual effect of nanoceria was found in the green alga with slight stimulation at low concentrations and strong inhibition at the highest concentrations tested. Chlorophyll a fluorescence experiments indicated that nanoceria had a significant impact on the primary photochemical processes of photosystem II. The primary cause of the observed photosynthetic inhibition by nanoceria is an excessive level of ROS formation; the results indicated a strong generation of reactive oxygen species (ROS) which caused oxidative damage, as evidenced by lipid peroxidation in both photosynthetic organisms. It is proposed that nanoceria can increase the production of hydrogen peroxide (a normal ROS by-product of light-driven photosynthesis) in both the green alga and the cyanobacterium; through an oxidative reaction, these ROS cause lipid peroxidation, compromising membrane integrity and also seriously impairing photosynthetic performance, eventually leading to cell death.

Oxidative and photochemical processes for the removal of galaxolide and tonalide from wastewater.

Synthetic musks have been reported in wastewaters at concentrations as high as tens of micrograms per litre. The two most significant polycyclic musk fragrance compounds are 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (HHCB, trade name galaxolide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (AHTN, trade name tonalide®). We report the result of several irradiation and advanced oxidation processes carried out on samples of the effluent of a wastewater treatment plant located in Alcalá de Henares, Madrid. Wastewater samples were pre-ozonated and spiked with 500 ng/L of tonalide or galaxolide in order to obtain final concentrations in the same order as the raw effluent. The treatments assayed were ozonation with and without the addition of hydrogen peroxide (O3, O3/H2O2), ultraviolet (254 nm low pressure mercury lamp) and xenon-arc visible light irradiation alone and in combination with ozone (UV, O3/UV, Xe, O3/Xe) and visible light photocatalytic oxidation using a Ce-doped titanium dioxide photocatalyst performed under continuous oxygen or ozone gas bubbling (O2/Xe/Ce-TiO2, O3/Xe/Ce-TiO2). In all cases, samples taken at different contact times up to 15 min were analyzed. An analytical method based on stir bar sorptive extraction (SBSE), followed by comprehensive two-dimensional gas chromatography (SBSE-GC × GC-TOF-MS), was used for the automatic searching and evaluation of the synthetic musks and other nonpolar or semipolar contaminants in the wastewater samples. In all cases tonalide was more easily removed than galaxolide. The best results for the latter (more than 75% removal after 5 min on stream) were obtained from ozonation (O3) and visible light photocatalytic ozonation (O3/Xe/Ce-TiO2). A significant removal of both pollutants (∼60% after 15 min) was also obtained during visible light photocatalysis (O2/Xe/Ce-TiO2). UV radiation was able to deplete tonalide (+90%) after 15 min but only reduced the concentration of galaxolide to about half of its initial concentration. The toxicity of treated samples decreased for O3/UV and O3/Ce-TiO2, but increased during irradiation processes UV, Xe and Xe/Ce-TiO2. Ozone treatments tend to decrease toxicity up to a certain dosage, from which point the presence of toxic transformation products has adverse effects on aquatic microorganisms.