Durable and rechargeable antimicrobial cotton driven by enhanced UV stability and real-time detection of biocidal factors.

In this study, graphene oxide/N-halamine nanocomposite was synthesized through Pickering miniemulsion polymerization, which was then coated on cotton surface. The modified cotton exhibited excellent superhydrophobicity, which could effectively prevent microbial infestation and reduce the probability of hydrolysis of active chlorine, with virtually no active chlorine released in water after 72 h. Deposition of reduced graphene oxide nanosheets endowed cotton with ultraviolet-blocking properties, attributing to enhanced UV adsorption and long UV paths. Moreover, encapsulation of polymeric N-halamine resulted in improved UV stability, thus extending the life of N-halamine-based agents. After 24 h of irradiation, 85 % of original biocidal component (active chlorine content) was retained, and approximately 97 % of initial chlorine could be regenerated. Modified cotton has been proven to be an effective oxidizing material against organic pollutants and a potential antimicrobial substance. Inoculated bacteria were completely killed after 1 and 10 min of contact time, respectively. An innovative and simple scheme for determination of active chlorine content was also devised, and real-time inspection of bactericidal activity could be achieved to assure antimicrobial sustainability. Moreover, this method could be utilized to evaluate hazard classification of microbial contamination in different locations, thus broadening the application scope of N-halamine-based cotton fabrics.

Photonic Hydrogels for Synergistic Visual Bacterial Detection and On-Site Photothermal Disinfection.

Rapid and sensitive diagnostics in the early stage of bacterial infection and immediate treatment play critical roles in the control of infectious diseases. However, it remains challenging to develop integrated systems with both rapid detection of bacterial infection and timely on-demand disinfection ability. Herein, we demonstrate a photonic hydrogel platform integrating visual diagnosis and on-site photothermal disinfection by incorporating Fe3O4@C nanoparticles into a poly(hydroxyethyl methacrylate)-co-polyacrylamide (PHEMA-co-PAAm) matrix. In vitro experiments demonstrate that such a hydrogel can respond to pH variation caused by bacterial metabolism and generate the corresponding color changes to realize naked-eye observation. Meanwhile, its excellent photothermal conversion ability enables it to effectively kill bacteria by destroying cell membranes under near-infrared irradiation. Moreover, the pigskin infection wound model also verifies the bacterial detection performance and disinfection ability of the hydrogel in vivo. Our strategy demonstrates a new approach for visual diagnosis and treatment of bacterial infections.

Quantitative Determination of Dark and Light-Activated Antimicrobial Activity of Poly(Phenylene Ethynylene), Polythiophene, and Oligo(Phenylene Ethynylene) Electrolytes.

Much recent effort has been directed toward the development of novel antimicrobial materials able to defeat new and antibiotic resistant pathogens. In this report, we study the efficacy of cationic poly(phenylene ethynylene), polythiophene, and oligo(phenylene ethynylene) electrolytes against laboratory strains of Pseudomonas aeruginosa, Staphylococcus aureus and Staphylococcus epidermidis. The focus of the study is to quantitatively evaluate the speed and extent of dark and light-activated antimicrobial activity. Using cell plating with serial dilutions, we determined that planktonic bacteria suspensions exposed to the antimicrobials (at 10 µg/mL) result in several log kills at 10 min both in the dark and under UV irradiation (360 nm) for all eight synthetic antimicrobials. However, there are significant differences in the ease of killing the different pathogens. In most trials, there is significantly greater killing under light-irradiation, indicating these materials may be used as versatile disinfectants.

TiO2-coated 2D photonic crystals for reflectometric determination of malachite green.

A "detect and destroy" strategy is reported for the spectroscopic determination and photocatalytic degradation of Malachite Green (MG) in aqueous solutions. The intensity of the reflection peak maxima from the TiO2-coated 2D-photonic crystal (PhC) at 633 nm wavelength undergoes a gradual decrease with increasing concentrations of MG. The determination of MG was readily achieved in the nanomolar range due to the quenching of the reflection intensity of the peak, measured using a fiber optic probe. The assay works in the 1.0 nM to 10 µM MG concentration range with a detection limit of 1.3 nM. The same TiO2-coated 2D-PhC surface can photocatalytically degrade MG in aqueous solutions under UV irradiation. The photocatalytic degradation in the presence of TiO2-coated 2D-PhC becomes evident as the blue color of MG changes to colorless with increasing irradiation time. The decrease in absorption is detected at 617 nm. It was found that the photocatalytic efficiency of TiO2 was synergistically enhanced in the presence of 2D-PhCs. It is concluded that each component of the TiO2-coated 2D-PhC system plays a key role in the detection and degradation of MG. Graphical abstractSchematic representation for reflectometric detection and photocatalytic degradation of hazardous Malachite Green dye using TiO2-coated two-dimensional photonic crystals.

Impact of UV irradiation on Chlorella sp. damage and disinfection byproducts formation during subsequent chlorination of algal organic matter.

The frequent occurrence of algal blooms in surface water has attracted more and more attention, which caused many water quality problems, including disinfection byproducts (DBPs). Algal organic matter (AOM) including intracellular organic matter (IOM) and extracellular organic matter (EOM), was a well-known precursor to DBPs formation in drinking water. This study evaluated the effect of ultraviolet (UV) irradiation on the cell integrity, IOM release and DBPs formation during subsequent chlorination of Chlorella sp. Results showed the damage rates of algal cells increased to 40.1% after the high UV irradiation of 528 mJ/cm2, which contributed to the release of IOM. In addition, UV irradiation was effective in reducing the formation of haloacetic acids (HAAs) both in AOM and IOM, but promoted the formation of nitrogenous DBPs (N-DBPs) from AOM in subsequent chlorination. Furthermore, neutral pH exerted a positive effect on the formation of DBPs. UV irradiation decreased the bromine substitution factor (BSF) value of AOM at a high bromide level. The BSF values increased with increasing of the concentration of bromide. Moreover, more amino acids and low molecular weight precursors were produced after UV irradiation in filtered supernatant, which contributed to the formation of N-DBPs with algal chlorination. Overall, this information demonstrated pre-oxidation of UV irradiation could be used to treat the algal-rich drinking water.

Sunlight caused interference in outdoor N, N-diethyl-p-phenylenediamine colorimetric measurement for residual chlorine and the solution for on-site work.

Chlorination is the most common method to control water qualities, in some case on-site outdoor measurements are required to measure easily-decaying residual chlorine concentration appropriately without delay. In this study sunlight-induced unexpected colour development (UCD) of N, N-diethyl-p-phenylenediamine (DPD) colorimetric measurement was studied under several sun exposure conditions. The colour development level was evaluated with reference to chlorine concentration (mg/L) and relationships between colour development rate (mg/L min) and intensities of solar were investigated. UCD was found to be related to both exposure intensity and time. By means of exposure experiment under specific wavelength of ultraviolet (UV), it was confirmed that both middle and short wavelength of UV radiation being responsible for such an unexpected measurement. Consequently, a simple device was designed using three commercially available anti-UV films, one of which could effectively prevent the UCD from direct sun exposure.

Solar photolysis of soluble microbial products as precursors of disinfection by-products in surface water.

In the Pearl River Delta area, the upstream municipal wastewater is commonly discharged into rivers which are a pivotal source of downstream drinking water. Solar irradiation transforms some of the dissolved organic matter discharged from the wastewater, also affecting the formation of disinfection by-products in subsequent drinking water treatment plants. The effect of simulated solar radiation on soluble microbial products extracted from activated sludge was documented in laboratory experiments. Irradiation was found to degrade macromolecules in the effluent, yielding smaller, more reactive intermediate species which reacted with chlorine or chloramine to form higher levels of noxious disinfection by-products. The soluble microbial products were found to be more active in formation of disinfection by-products regard than naturally-occurring organic matter. The results show that solar irradiation induced the formation of more trihalomethane (THMs), chloral hydrate (CH) and trichloronitromethane (TCNM), causing greater health risks for downstream drinking water.

Solar light irradiation significantly reduced cytotoxicity and disinfection byproducts in chlorinated reclaimed water.

Chlorinated reclaimed water is widely used for landscaping and recreational purposes, resulting in human exposure to toxic disinfection byproducts. Although the quality of chlorinated reclaimed water might be affected by sunlight during storage, the effects of solar light irradiation on the toxicity remain unknown. This study investigated the changes in cytotoxicity and total organic halogen (TOX) of chlorinated reclaimed water exposed to solar light. Irradiation with solar light for 12 h was found to significantly reduce the cytotoxicity of chlorinated reclaimed water by about 75%, with ultraviolet light being responsible for the majority of this reduction. Chlorine residual in reclaimed water tended to increase the cytotoxicity, and the synergy between solar light and free chlorine could not enhance the reduction of cytotoxicity. Adding hydroxyl radical scavengers revealed that the contribution of hydroxyl radical to cytotoxicity reduction was limited. Solar light irradiation concurrently reduced TOX. The low molecular weight (<1 kDa) fraction was the major contributor of cytotoxicity and TOX in chlorinated reclaimed water. Detoxification of the low molecular weight fraction by light irradiation was mainly a result of TOX dehalogenation, while detoxification of the high molecular weight (>1 kDa) fraction was probably caused by photoconversion from high toxic TOX to low toxic TOX.

Comparative study on DBPs formation profiles of intermediate organics from hydroxyl radicals oxidation of microbial cells.

This study assessed the characteristics of disinfection byproducts (DBPs) formation from intermediate organics during UV/H2O2 treatment of activated sludge and algae cells under various reaction conditions. The DBPs including trihalomethanes (THMs), haloacetic acids (HAAs), haloketones (HKs) and haloacetonitriles (HANs) in UV/H2O2-treated and chlorinated water were measured. The results showed that both dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) increased during the initial stage of UV/H2O2 treatment due to the lysis of sludge and algae cells, which enhanced the formation of both C- and N-DBPs; however, both DOC and DON decreased after longer reaction times. During the UV/H2O2 treatments, THMs formation potential (THMFP) peaked earlier than did HAAs formation potential (HAAFP). This shows that the dissolved organics released from lysis of microbial cells in the early stages of oxidation favor the production of THMs over HAAs; however, HAAs precursors increased with the oxidation time. Chlorination with bromide increased the formation of THMs and HAAs but less HKs and HANs were produced. Comparisons of normalized DBP formation potential (DBPFP) of samples collected during UV/H2O2 treatments of four different types of organic matter showed that the highest DBPFP occurred in filtered treated wastewater effluent, followed by samples of activated sludge, filtered eutrophicated pond water, and samples of algae cells. With increasing oxidation time, the dominant DBP species shifted from THMs to HAAs in the samples of activated sludge and algae cells. The DBPFP tests also showed that more HAAs were formed in biologically treated wastewater effluent, while the eutrophicated source water produced more THMs.

Effect of gaseous ozone and light-activated disinfection on the surface hardness of resin-based root canal sealers.

Although root canal instruments remove most of the content from the main root canal space, disinfection or irrigation plays an indispensable role in all areas of the root canal system, especially in parts that are inaccessible by instruments. The originality of this study was to investigate the effect of two novel disinfection techniques on the surface hardness of resin-based endodontic sealers using atomic force microscopy (AFM). Forty extracted single-rooted maxillary central human teeth were prepared and divided into four groups according to treatment methods. The first group was irrigated with saline and served as a control, other groups irrigated with sodium hypochlorite (NaClO); gaseous ozone; and light-activated disinfection (LAD). The groups were divided into two subgroups, according to the obturation method used: subgroup A: gutta-percha and AH plus; and subgroup B: EndoREZ/resin-coated cones. After obturation, atomic force microscopy (AFM) measurement was performed to analyze the surface hardness of the sealers. There was a significant difference between group 1A and group 3A (p < 0.05). Group 3B had the highest surface hardness values that were statistically different (p < 0.05). When disregarding the sealers, the ozone possessed statistically higher surface hardness values than the other groups in all root thirds (p < 0.05). The use of ozone and LAD may alter the surface hardness of resin-based sealers. The use of AFM can be considered an alternative hardness test techonology for sealing material.

Perchlorate production by photodecomposition of aqueous chlorine solutions.

Aqueous chlorine solutions (defined as chlorine solutions (Cl(2,T)) containing solely or a combination of molecular chlorine (Cl(2)), hypochlorous acid (HOCl), and hypochlorite (OCl(-))) are known to produce toxic inorganic disinfection byproduct (e.g., chlorate and chlorite) through photoactivated transformations. Recent reports of perchlorate (ClO(4)(-)) production-a well-known thyroid hormone disruptor- from stored bleach solutions indicates the presence of unexplored transformation pathway(s). The evaluation of this potential ClO(4)(-) source is important given the widespread use of aqueous chlorine as a disinfectant. In this study, we perform detailed rate analysis of ClO(4)(-) generation from aqueous chlorine under varying environmental conditions including ultraviolet (UV) light sources, intensity, solution pH, and Cl(2,T) concentrations. Our results show that ClO(4)(-) is produced upon UV exposure of aqueous chlorine solutions with yields ranging from 0.09 × 10(-3) to 9.2 × 10(-3)% for all experimental conditions. The amount of ClO(4)(-) produced depends on the starting concentrations of Cl(2,T) and ClO(3)(-), UV source wavelength, and solution pH, but it is independent of light intensity. We hypothesize a mechanistic pathway derived from known reactions of Cl(2,T) photodecomposition that involves the reaction of Cl radicals with ClO(3)(-) to produce ClO(4)(-) with calculated rate coefficient (k(ClO4-)) of (4-40) × 10(5) M(-1) s(-1) and (3-250) × 10(5) M(-1) s(-1) for UV-B/C and UV-A, respectively. The measured ClO(4)(-) concentrations for both UV-B and UV-C experiments agreed well with our model (R(2) = 0.88-0.99), except under UV-A light exposure (R(2) = 0.52-0.93), suggesting the possible involvement of additional pathways at higher wavelengths. Based on our results, phototransformation of aqueous chlorine solutions at concentrations relevant to drinking water treatment would result in ClO(4)(-) concentrations (~0.1 µg L(-1)) much below the proposed drinking water limits. The importance of the hypothesized mechanism is discussed in relation to natural ClO(4)(-) formation by atmospheric transformations.

Bactericidal effects and mechanisms of visible light-responsive titanium dioxide photocatalysts on pathogenic bacteria.

This review focuses on the antibacterial activities of visible light-responsive titanium dioxide (TiO(2)) photocatalysts. These photocatalysts have a range of applications including disinfection, air and water cleaning, deodorization, and pollution and environmental control. Titanium dioxide is a chemically stable and inert material, and can continuously exert antimicrobial effects when illuminated. The energy source could be solar light; therefore, TiO(2) photocatalysts are also useful in remote areas where electricity is insufficient. However, because of its large band gap for excitation, only biohazardous ultraviolet (UV) light irradiation can excite TiO(2), which limits its application in the living environment. To extend its application, impurity doping, through metal coating and controlled calcination, has successfully modified the substrates of TiO(2) to expand its absorption wavelengths to the visible light region. Previous studies have investigated the antibacterial abilities of visible light-responsive photocatalysts using the model bacteria Escherichia coli and human pathogens. The modified TiO(2) photocatalysts significantly reduced the numbers of surviving bacterial cells in response to visible light illumination. They also significantly reduced the activity of bacterial endospores; reducing their toxicity while retaining their germinating abilities. It is suggested that the photocatalytic killing mechanism initially damages the surfaces weak points of the bacterial cells, before totally breakage of the cell membranes. The internal bacterial components then leak from the cells through the damaged sites. Finally, the photocatalytic reaction oxidizes the cell debris. In summary, visible light-responsive TiO(2) photocatalysts are more convenient than the traditional UV light-responsive TiO(2) photocatalysts because they do not require harmful UV light irradiation to function. These photocatalysts, thus, provide a promising and feasible approach for disinfection of pathogenic bacteria; facilitating the prevention of infectious diseases.

Impact of UV disinfection combined with chlorination/chloramination on the formation of halonitromethanes and haloacetonitriles in drinking water.

The application of UV disinfection in water treatment is increasing due to both its effectiveness against protozoan pathogens, and the perception that its lack of chemical inputs would minimize disinfection byproduct formation. However, previous research has indicated that treatment of nitrate-containing drinking waters with polychromatic medium pressure (MP), but not monochromatic (254 nm) low pressure (LP), UV lamps followed by chlorination could promote chloropicrin formation. To better understand this phenomenon, conditions promoting the formation of the full suite of chlorinated halonitromethanes and haloacetonitriles were studied. MP UV/postchlorination of authentic filter effluent waters increased chloropicrin formation up to an order of magnitude above the 0.19 µg/L median level in the U.S. EPA's Information Collection Rule database, even at disinfection-level fluences (<300 mJ/cm(2)) and nitrate/nitrite concentrations (1.0 mg/L-N) relevant to drinking waters. Formation was up to 2.5 times higher for postchlorination than for postchloramination. Experiments indicated that the nitrating agent, NO(2)(•), generated during nitrate photolysis, was primarily responsible for halonitromethane promotion. LP UV treatment up to 1500 mJ/cm(2) did not enhance halonitromethane formation. Although MP UV/postchloramination enhanced dichloroacetonitrile formation with Sigma-Aldrich humic acid, formation was not significant in field waters. Prechlorination/MP UV nearly doubled chloropicrin formation compared to MP UV/postchlorination, but effects on haloacetonitrile formation were not significant.

A new generation of biocides for control of crustacea in fish farms.

Farming of salmon has become a significant industry in many countries over the past two decades. A major challenge facing this sector is infestation of the salmon by sea lice. The main way of treating salmon for such infestations is the use of medicines such as organophosphates, pyrethrins, hydrogen peroxide or benzoylphenyl ureas. The use of these medicines in fish farms is, however, highly regulated due to concerns about contamination of the wider marine environment. In this paper we report the use of photochemically active biocides for the treatment of a marine copepod, which is a model of parasitic sea lice. Photochemical activation and subsequent photodegradation of PDAs may represent a controllable and environmentally benign option for control of these parasites or other pest organisms in aquaculture.

Conjugated polyelectrolyte capsules: light-activated antimicrobial micro "Roach Motels".

Microcapsules consisting of alternating layers of oppositely charged poly(phenylene ethynylene)-type conjugated polyelectrolytes (CPEs) were prepared via layer-by-layer deposition onto MnCO3 template particles followed by dissolution of the template particles using an ethylenediaminetetraacetate solution. The resulting microcapsules exhibit bright-green fluorescence emission characteristics of the CPEs. Strong antimicrobial activity was observed upon mixing of polyelectrolyte capsules with Cobetia marina or Pseudomonas aeruginosa followed by white-light irradiation. It was demonstrated that the materials act as highly effective light-activated micro "Roach Motels" with greater than 95% kill after exposure to approximately 1 h of white light.

Impact of simulated solar irradiation on disinfection byproduct precursors.

The Sacramento-San Joaquin Delta is the major drinking water source for 23 million California residents. Consequently, many studies have examined disinfection byproduct (DBP) formation in relation to Delta dissolved organic carbon (DOC) concentration. However, DOC characteristics within the Delta are not the same as those entering downstream water treatment facilities. As water is transferred to Southern California through the California Aqueduct, a 714.5 km-open channel, it is exposed to sunlight, potentially altering DBP precursors. We collected water from three sites within the Delta and one nearthe California Aqueduct, representing different DOC sources, and irradiated them in a solar simulator at a dose equivalent to that received during four days conveyance in the aqueduct. Photolytic changes in DOC were assessed by measuring CO2 and organic acid production, fluorescence, and ultraviolet absorbance over time. Trihalomethane (THM) and haloacetic acid (HAA) formation potentials, as well as the distribution of hydrophobic, transphilic, and hydrophilic acid fractions were determined at exposures equivalent to one and four days. Solar irradiation significantly decreased ultraviolet absorbance and fluorescence intensity, produced organic acids, and increased the hydrophilic fraction of waters. These changes in DOC caused a shift in bromine incorporation among the THM and HAA species. Our results are the first to demonstrate the importance of sunlight in altering DOC with respect to DBP formation.

Investigation and modeling of solar UV-induced chlorine decay in disinfection contact basins at full-scale wastewater treatment plants.

Residual chlorine loss due to UV sunlight in the chlorine disinfection contact basins (DCBs) was investigated at two full-scale wastewater treatment plants (WWTPs). Chlorine decay due to solar UV-induced photochemical reaction was found to be significant and had diurnal and seasonal variations. The total chlorine loss due to sunlight ranged from 19 to 26% of the total chlorine chemical use at the two plants studied. Covering chlorine contact basins led to more stable chlorine demand regardless of the diurnal and seasonal sunlight intensity. Therefore, covering chlorine contact basins offers more stable, or accurate, chlorine dosage and effluent residual control and requires less effort by plant operators. A mathematical model was developed to calculate the amount of UV-induced chlorine decay. The model developed can be used to estimate the UV-induced chlorine decay rate and total chlorine loss due to sunlight at WWTPs with various basin configurations, flowrates, chlorine dosages, and geographical locations. The model results allow the capital cost of covering needs to be assessed against the chlorine chemical cost savings.

Abiotic degradation of triphenylborane pyridine (TPBP) antifouling agent in water.

The abiotic degradation of the new antifouling agent, triphenylborane pyridine (TPBP), was investigated in buffer solutions having different pH values (pH 5, 7, and 9), and in artificial and natural seawater to estimate environmental fate of TPBP. The TPBP in these waters was decomposed by a seven-day hydrolysis process at 50 degrees C both in the dark and a photolysis process under UV-A irradiation using a high-pressure mercury lamp for periods up to 24h. TPBP hydrolysis was significantly enhanced by acidic pH solutions. The photolysis rate of TPBP was higher in acidic pH solutions than in neutral or basic pH solutions, and was highest in natural seawater, which could have contained naturally dissolved organic matter. Two degradation products, phenol and an unknown substance (Peak #1), were observed during the hydrolysis and photolysis studies of TPBP. The concentration of these substances after a one-day photolysis treatment was higher than after a seven-day hydrolysis treatment. The degradation rate of TPBP in the five test water samples was related to the simultaneous photolysis formation of phenol and Peak #1. However, the degradation rate of TPBP was not related to the formation of the hydrolysis products. Therefore, it is suggested that photodegradation of TPBP follows a different pathway to the hydrolysis degradation of TPBP. Our results indicate the chemical and photochemical reaction of TPBP in water occurs in natural aquatic environments.

Comparison of temporal changes in components of formalin guaiacol under several storage conditions.

This study examined the effects of storage conditions such as time course, temperature, fluorescent light, and darkness on the components and antibacterial activity of formalin guaiacol (FG) used in endodontic treatment. We measured the quantities of formaldehyde and guaiacol in FG and antibacterial activities against Staphylococcus aureus, Porphyromonas gingivalis, and Porphyromonas endodontalis. The components and antibacterial activity of FG in the brown or transparent tightly sealed containers were not affected by temperature or fluorescent light throughout the 4 week test. However, in the loosely sealed containers, formaldehyde and guaiacol in FG sample decreased remarkably within one week, not only in a temperature- and time-dependent manner, but also under fluorescent light at 20 degrees C. Furthermore, the antibacterial activities in the FG sample were significantly attenuated in parallel with the decrease in formaldehyde levels. Fluorescent light caused color changes and crystallization of FG samples in the transparent containers. These results suggest that it is important to replace fresh FG every 5 to 7 days for endodontic treatment and that, in the dental office, it is advisable to store fresh FG in tightly sealed containers every 2 weeks to maintain its efficacy.