Inactivation of Escherichia coli by sonoelectrocatalytic disinfection using TiO2 as electrode

This is the first study to demonstrate sonoelectrocatalytic disinfection using titanium dioxide (TiO₂) as an anode for effective inactivation of Escherichia coli. In brief, a non-woven TiO₂ fabric used as an anode and a platinum cathode were immersed in an E. coli suspension in which a positive potential was applied to TiO₂ concomitant with ultrasound (US) irradiation. Two control experiments were performed using E. coli suspensions to exhibit the effects of the sonoelectrocatalytic disinfection. One was disinfection by applying a positive potential to a TiO₂ electrode, but without US irradiation (electrochemical disinfection). The other was disinfection without applying a potential, but with US irradiation in the presence of TiO₂ (sonocatalytic disinfection). The cell inactivation rate in sonoelectrocatalytic disinfection was synergistically much more enhanced than the combined inactivation rates in electrochemical disinfection and sonocatalytic disinfection. This synergistically enhanced inactivation rate of E. coli cells was attributable to effective reaction of the sonocatalytically generated OH radicals with E. coli cells at the surface of the TiO₂ anode, which resulted from the electroadsorption of E. coli cells toward the TiO₂ anode.     

Enhanced OH radical generation by dual-frequency ultrasound with TiO2 nanoparticles: Its application to targeted sonodynamic therapy

The present study demonstrated the enhanced hydroxyl (OH) radical generation by combined use of dual-frequency (0.5 MHz and 1 MHz) ultrasound (US) and titanium dioxide (TiO₂) nanoparticles (NPs) as sonocatalyst. The OH radical generation became the maximum, when 0.5 MHz US was irradiated at an intensity of 0.8 W/cm² and 1 MHz US was irradiated at intensities at 0.4 W/cm² in the presence of TiO₂ NPs under the examined conditions. After incorporation of TiO₂ NPs modified with targeting protein pre-S1/S2, HepG2 cancer cells were subjected to the dual-frequency US at optimum irradiation intensities (“targeted-TiO₂/dual-US treatment”). Growth of the HepG2 cells was reduced by 46% compared with the control condition after irradiation of dual-frequency US for 60 s with TiO₂ NPs incorporation. In contrast, HepG2 cell growth was almost the same as that in the control condition when cells were irradiated with either 0.5 MHz or 1 MHz ultrasound alone without TiO₂ NP incorporation.     

Inactivation of Pathogenic Microorganisms in the Photocatalytic Process on Nanosized TiO2 Crystals

The kinetics of the photocatalytic oxidation of E. coli gram-negative bacteria and the basic components of the cell wall membrane (LPS, PE, and PGN) on a porous film composed of TiO₂ nanoparticles was studied using frustrated total internal reflection FTIR spectroscopy. Structural changes in the cell wall membrane at the initial stage of cell oxidation were revealed. It was demonstrated that the cell’s organic material is photocatalytically oxidized in such a manner that the TiO₂ surface is cleaned. Laser photolysis experiments demonstrated that the organic material of the cell wall membrane reduces holes in the valence band of TiO₂.     

Investigation of Mg(OH)2 nanoparticles as an antibacterial agent

Our experimental results of using Mg(OH)₂ nanoparticles as an antibacterial agent are reported in this study. The antibacterial behavior of Mg(OH)₂ nanoparticles in liquid culture and in paper sheets was investigated. The colony forming units (CFU) counting and the headspace gas chromatography (HS-GC) measurement were used to determine the cell viability. Results indicate that Mg(OH)₂ nanoparticles are effective antibacterial agent against Escherichia coli (E. coli) and Burkholderia phytofirmans, and the OH^? and Mg²⁺ ions in Mg(OH)₂ water suspension were found not to be the reason for killing the bacteria. Mg(OH)₂ nanoparticles could be added directly to wood pulp to make paper sheets, whose antibacterial efficiency increased with the increase of the nanoparticle amount. The possible mechanism of antibacterial effect of Mg(OH)₂ nanoparticles is discussed.     

Sonocatalytic injury of cancer cells attached on the surface of a nickel–titanium dioxide alloy plate

The present study demonstrates ultrasound-induced cell injury using a nickel–titanium dioxide (Ni–TiO₂) alloy plate as a sonocatalyst and a cell culture surface. Ultrasound irradiation of cell-free Ni–TiO₂ alloy plates with 1 MHz ultrasound at 0.5 W/cm² for 30 s led to an increased generation of hydroxyl (OH) radicals compared to nickel–titanium (Ni–Ti) control alloy plates with and without ultrasound irradiation. When human breast cancer cells (MCF-7 cells) cultured on the Ni–TiO₂ alloy plates were irradiated with 1 MHz ultrasound at 0.5 W/cm² for 30 s and then incubated for 48 h, cell density on the alloy plate was reduced to approximately 50% of the controls on the Ni–Ti alloy plates with and without ultrasound irradiation. These results indicate the injury of MCF-7 cells following sonocatalytic OH radical generation by Ni–TiO₂. Further experiments demonstrated cell shrinkage and chromatin condensation after ultrasound irradiation of MCF-7 cells attached on the Ni–TiO₂ alloy plates, indicating induction of apoptosis.     

Preparation, characterization and visible-light photocatalytic activity of AgI/AgCl/TiO2

In this paper, a novel composite photocatalyst AgI/AgCl/TiO₂ was prepared by ion exchange method and characterized by XRD, SEM and UV-Vis spectrometry. The as-prepared AgI/AgCl/TiO₂ composites show much higher photocatalytic activity than AgCl/TiO₂ and AgI/TiO₂ under visible-light irradiation (λ > 400 nm) in the process of methyl orange (MO) degradation. When the molar percentage of AgI to initial AgCl is 20% (sample SE-20%), the maximal degradation efficiency of MO has reached 85.8% after irradiation for 120 min. The enhancement of photocatalytic activity of the composite photocatalyst AgI/AgCl/TiO₂ will be attributed to its good absorption in the visible-light region, especially low recombination rate of the electron-hole pairs based on the photoluminescence (PL) spectra investigation of AgI/AgCl/TiO₂ and the matching band structures of AgI, AgCl and TiO₂. The detection of reactive species by radical scavengers displays that O₂⁻ and H₂O₂ are the main reactive species for the degradation of MO under visible-light irradiation. Moreover, PL analysis by using terephthalic acid (TA) as a probe molecule further reveals that OH can be negligible for the degradation of MO.     

Conductive diamond sono-electrochemical disinfection (CDSED) for municipal wastewater reclamation

In the present work, the disinfection of actual effluents from a municipal wastewater treatment plant (WWTP) by a conductive diamond sono-electrochemical process was assessed. First, efficiency of single electrodisinfection process with diamond anodes (without the contribution of ultrasounds) was studied, finding that the total disinfection can be attained at current charges applied below 0.02 kA h m⁻³. It was also found that the main disinfection mechanism is the attack of Escherichia coli (E. coli) by the disinfectants produced in the electrochemical cell and that the production of chlorates is avoided when working at current densities not higher than 1.27 A m⁻². Next, a marked synergistic effect was found when coupling ultrasound (US) irradiation to the electrochemical system (sono-electrochemical disinfection). This increase in the disinfection rate was found to be related to the suppression of the agglomeration of E. coli cells and the enhancement in the production of disinfectant species.     

Photocatalytic inactivation of Gram-positive and Gram-negative bacteria by reactive plasma processed nanocrystalline TiO2 powder

Nanocrystalline TiO₂ powder is synthesized using a novel reactive plasma process in which the precursor TiH₂ powder is oxidized through thermal plasma in-flight route to generate nanocrystalline TiO₂ powder. The synthesized powder consists of nano-sized TiO₂ particles, both anatase and rutile phases, in which anatase is the predominant phase. An additional feature of the plasma synthesized TiO₂ powder is the higher surface concentration of Ti³⁺ state and hydroxyl group that enhance its photocatalytic activity. The photocatalytic inactivation of Gram-positive Enterococcus and Gram-negative Klebsiella bacteria is studied using the plasma synthesized TiO₂ nanopowder with 365 nm ultraviolet (UV) light. The mechanism behind the photocatalytic disinfection of bacteria is discussed. The plasma synthesized TiO₂ nanopowder catalyst is found effective in killing Enterococcus and Klebsiella. The results corroborated that the plasma synthesized TiO₂ powder can be used for waste water treatment and water purification.     

Enhanced sonodynamic therapy by carbon dots-shelled microbubbles with focused ultrasound

Sonodynamic therapy involving the non-invasive and local generation of lethal reactive oxygen species (ROS) via ultrasound (US) with sonosensitizers has been proposed as an emerging tumor therapy strategy. However, such therapy is usually associated with inertial cavitation and unnecessary damage to healthy tissue because current sonosensitizers have insufficient sensitivity to US. Here, we report the use of a new proposed sonosensitizer, carbon dots (C-dots), to assemble microbubbles with a gas core (C-dots MBs). As the C-dots were directly integrated into the MB shell, they could effectively absorb the energy of inertial cavitation and transfer it to ROS. Our results revealed the appearance of ¹O₂, •OH, and H₂O₂ after US irradiation of C-dots MBs. In in vitro experiments, treatment with C-dots MBs plus US induced lipid peroxidation, elevation of intracellular ROS, and apoptosis in 32.5%, 45.3%, and 50.1% of cells respectively. In an animal solid tumor model, treatment with C-dots MBs plus US resulted in a 3-fold and 2.5-fold increase in the proportion of ROS-damaged cells and apoptotic cells, respectively, compared to C-dots MBs alone. These results will pave the way for the design of novel multifunctional sonosensitizers for SDT tumor therapy.     

Sonosynthesis of nano TiO2 on wool using titanium isopropoxide or butoxide in acidic media producing multifunctional fabric

This study presents a novel idea to prepare nanocrystalline structure of TiO₂ under ambient pressure at 60–65 °C using in situ sonochemical synthesis by hydrolysis of either titanium isopropoxide or titanium butoxide in an acidic aqueous solution. The nano titanium dioxide coated wool fabrics possess significant antibacterial/antifungal activity and self-cleaning property by discoloring Methylene blue stain under sunlight irradiation. This process has no negative effect on cytotoxicity and tensile strength of the sonotreated fabric even reduces alkaline solubility and photoyellowing and improves hydrophilicity. More titanium isopropoxide or titanium butoxide as a precursor led to higher photocatalytic activities of the treated fabrics. Also introducing more ethanol improved the adsorption of TiO₂ on the wool fabric surface leading to enhanced photocatalytic activity. EDS and XRD patterns, SEM images, X-ray mapping confirmed the presence of nano TiO₂ particles on the fabric surface. The role of both solvent and precursor concentrations on the various properties of the fabric was investigated and the optimized conditions were obtained using response surface methodology.     

Targeted sonodynamic therapy using protein-modified TiO2 nanoparticles

Our previous study suggested new sonodynamic therapy for cancer cells based on the delivery of titanium dioxide (TiO₂) nanoparticles (NPs) modified with a protein specifically recognizing target cells and subsequent generation of hydroxyl radicals from TiO₂ NPs activated by external ultrasound irradiation (called TiO₂/US treatment). The present study first examined the uptake behavior of TiO₂ NPs modified with pre-S1/S2 (model protein-recognizing hepatocytes) by HepG2 cells for 24 h. It took 6 h for sufficient uptake of the TiO₂ NPs by the cells. Next, the effect of the TiO₂/US treatment on HepG2 cell growth was examined for 96 h after the 1 MHz ultrasound was irradiated (0.1 W/cm², 30 s) to the cells which incorporated the TiO₂ NPs. Apoptosis was observed at 6 h after the TiO₂/US treatment. Although no apparent cell-injury was observed until 24 h after the treatment, the viable cell concentration had deteriorated to 46% of the control at 96 h. Finally, the TiO₂/US treatment was applied to a mouse xenograft model. The pre-S1/S2-immobilized TiO₂ (0.1 mg) was directly injected into tumors, followed by 1 MHz ultrasound irradiation at 1.0 W/cm² for 60 s. As a result of the treatment repeated five times within 13 days, tumor growth could be hampered up to 28 days compared with the control conditions.     

TiO2 nanotubes: photocatalyst for cancer cell killing

The present work reports on the use of self‐organized TiO₂ nanotube layers for the photocatalytic killing of cancer cells. TiO₂ nanotube layers with different dimensions (diameter 50 nm and 100 nm, thickness 800 nm and 1.3 μm, respectively) were grown by anodization of Ti. Upon low dose of UV irradiation, the vitality of cancer cells cultured on these nanotube layers was significantly affected – the cells reduced their shape and size and a significant amount of the dead cells was found. These results demonstrate that self‐organized TiO₂ nanotube layers can be used for photo‐induced cancer cell killing. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of photo-induced superhydrophilicity of titanium dioxide nanoparticles on the anti-fouling performance of ultrafiltration membranes

Fouling is one of the most present prominent problems in almost all membrane processes. An increase in the membrane hydrophilicity is one of the effective ways to improve the membrane resistance to fouling. In this research, TiO₂ nanoparticles were deposited on the surface of composite ultrafiltration (UF) membrane, and then irradiated by ultraviolet (UV) light. The coating of the membrane surface with TiO₂ nanoparticles and radiation with (UV) light led to the considerable increase of hydrophilicity on the membrane surface. The deposition of TiO₂ nanoparticles was carried out through coordinance bonds with OH functional groups of the polymer on the membrane surface. The flux through a coated and (UV) light radiated membrane was increased to a large extent compared to a virgin membrane. In this research, the effect of different concentrations of TiO₂ nanoparticles in the presence and absence of (UV) irradiation was investigated, and the role of increasing of hydrophilicity on the anti-fouling property of membranes was studied. In order to characterize the membranes FTIR, XRD, SEM, water contact angle and cross-flow filtration were employed. This procedure is a useful technique for improvement of hydrophilicity to decrease (increase) fouling (anti-fouling performance) and enhance the permeation of membranes.     

Sonocatalytic and sonophotocatalytic degradation of rhodamine 6G containing wastewaters

The present work deals with degradation of aqueous solution of Rhodamine 6G (Rh 6G) using sonocatalytic and sonophotocatalytic treatment schemes based on the use of cupric oxide (CuO) and titanium dioxide (TiO₂) as the solid catalysts. Experiments have been carried out at the operating capacity of 2 L and constant initial pH of 12.5. The effect of catalyst loading on the sonochemical degradation has been investigated by varying the loading over the range of 1.5–4.5 g/L. It has been observed that the maximum degradation of 52.2% was obtained at an optimum concentration of CuO as 1.5 g/L whereas for TiO₂ maximum degradation was observed as 51.2% at a loading of 4 g/L over similar treatment period. Studies with presence of radical scavengers such as methanol (CH₃OH) and n-butanol (C₄H₉OH) indicated lower extents of degradation confirming the dominance of radical mechanism. The combined approach of ultrasound, solid catalyst and scavengers has also been investigated at optimum loadings to simulate real conditions. The optimal solid loading was used for studies involving oxidation using UV irradiations where 26.4% and 28.9% of degradation was achieved at optimal loading of CuO and TiO_2, respectively. Studies using combination of UV and US irradiations have also been carried out using the optimal concentration of the catalysts. It has been observed that maximum degradation of 63.3% is achieved using combined US and UV with TiO₂ (4 g/L) as the photocatalyst. Overall it can be said that the combined processes give higher extent of degradation as compared to the individual processes based on US or UV irradiations.     

Combined ultrasonic and gamma-irradiation to prepare TiO2@PET-g-PAAc fabric composite for self-cleaning application

The grafting of polyacrylic acid (PAAc) onto the fabric of Poly(ethyleneterephthalate) (PET) was loaded with TiO₂ by a mixture sonication of TiO₂ dispersed in AAc dissolved in acetone solvent. Ultrasonic irradiation was utilized as a tool for a good dispersion of TiO₂ onto the PET fabric. The grafted PET fabrics with acrylic acid AAc monomer were successfully obtained using gamma-ray induced graft polymerization, the degree of grafting PET-g-PAAc fiber was 105%. The chemical compositions and crystal structure of grafted TiO₂@PET-g-PAAc fabrics were characterized by ATR-FTIR and XRD. It was found that loading of PET fiber with in TiO₂ particles showing the formation of anatase and rutile as performed by XRD. The thermal property of TiO₂@PET-g-PAAc was investigated by differential thermal analysis (DTA). The obtained result indicated the thermal property of the grafted TiO₂@PET-g-PAAc was increased. Image of scanning electron microscope (SEM) indicated the good adherent and good distribution of PAAc and TiO₂ with PET fabric. The self-cleaning property of TiO₂@PET-g-PAAc has been evaluated by using three kinds of dyes as models.     

Disinfection effect of a continuous-flow ultrasound/ultraviolet baffled reactor at a pilot scale

An ultrasound/ultraviolet (US/UV) baffled reactor was developed to fill the gap in ultraviolet (UV) disinfection associated with disinfection efficiency. According to the previously selected operational condition, a continuous-flow US/UV baffled reactor was continuously operated in a wastewater treatment plant at a pilot scale for nearly three months, and the disinfection influent and effluent were analyzed, including fecal coliforms, Escherichia coli, and fecal streptococci. The US/UV baffled reactor could guarantee a high effluent disinfection performance in terms of fecal coliforms removal even with the fluctuation of the secondary effluent. All the disinfected effluents satisfied the requirement of the “Pollutants Discharge Standard of Municipal Wastewater Treatment Plant in China” (fecal coliforms below 1000 CFU/L for class 1A), and 87% of the tested fecal coliforms concentration in the disinfected effluent was below 100 CFU/L, nearly eliminating all fecal coliforms. Further analysis of the E. coli and fecal streptococci showed the broad disinfection ability and high disinfection efficiency of the US/UV baffled reactor. The flexibility of the specific energy consumption for the disinfection system depends on the water quality.     

Targeted sonocatalytic cancer cell injury using avidin-conjugated titanium dioxide nanoparticles

In this study, we applied sonodynamic therapy to cancer cells based on the delivery of titanium dioxide (TiO₂) nanoparticles (NPs) modified with avidin protein, which preferentially discriminated cancerous cells from healthy cells. Subsequently, hydroxyl radicals were generated from the TiO₂ NPs after activation by external ultrasound irradiation (TiO₂/US treatment). Although 30% of the normal breast cells (human mammary epithelial cells) exhibited the uptake of avidin-modified TiO₂ NPs, over 80% of the breast cancer cells (MCF-7) exhibited the uptake of avidin-TiO₂ NPs. Next the effect of the TiO₂/US treatment on MCF-7 cell growth was examined for up to 96 h after 1-MHz ultrasound was applied (0.1 W/cm², 30 s) to cells that incorporated the TiO₂ NPs. No apparent cell injury was observed until 24 h after the treatment, but the viable cell concentration declined to 68% compared with the control at 96 h.     

Radiation removal of lead and cadmium complexed with ethylenediamine tetraacetic ACID from aqueous solutions

The removal of lead (100 mg/L) and cadmium (27 mg/L) complexed with ethylenediamine tetraacetic acid (EDTA) in presence of different scavengers has been investigated. The experiments show that in acidic solutions, the EDTA complexed lead may be reduced at a dose of 40 kGy up to 97% without the addition of typical OH radical scavengers such as Na(K) formate. The addition of OH radical scavengers as 1×10⁻³ mol/L HCOOK, 2×10⁻³ mol/L carbonate or 2×10⁻³ mol/L bicarbonate (wide range of pH) results in no further improvement. The bubbling of the solution with nitrogen or oxygen also exhibits no positive effect. On the contrary, saturation with nitrous oxide in the presence of scavengers has a modest positive influence, whereas in the system which is scavenger-free, high negative effect (30 %) was observed. The presence of nitrate (e _aq ⁻ scavenger) appears to be important for an effective reduction of complexed lead. The efficient removal of cadmium complexed with EDTA proceeds up to 96 % at a dose of 40 kGy with an addition of 5×10⁻³ mol/L of carbonate as the OH radical scavenger and simultaneously pH buffer (pH 10.5). After irradiation, the cadmium is present in the final form of CdCO₃.     

In situ sonosynthesis of nano TiO2 on cotton fabric

Here, titanium dioxide nanoparticles (NPs) were sonosynthesized and loaded simultaneously onto the cotton fabric. Titanium tetra isopropoxide (TTIP) was used as precursor and ultrasonic irradiation was utilized as a tool for synthesis of TiO₂ in low temperature with anatase structure and loading nanoparticles onto the cotton fabric. TiO₂ loaded cotton fabric was characterized by XRD, FE-SEM, EDS, and XRF. Moreover, several properties of the treated cotton fabrics such as self-cleaning, UV protection, washing durability, and tensile strength were studied. The effect of variables, including TTIP concentration and sonication time, was investigated based on central composite design (CCD) and response surface methodology (RSM). The results confirmed formation of anatase TiO₂ nanoparticles with 3–6 nm crystalline size loaded onto the cotton fabric at low temperature (75 °C) that led to good self-cleaning and UV-protection properties. The excellent UV-protection rating of the treated fabric maintained even after 25 home launderings indicating an excellent washing durability. Interestingly, sonochemical method had no negative influence on the cotton fabric structure. The statistical analysis indicated significant effect of both TTIP concentration and sonication time on the content of the loaded TiO₂ on the fiber and self-cleaning properties of the fabric.     

Electrical sterilization of Escherichia coli by electrostatic atomization with a photo-chemical catalyst

The inactivation of Escherichia coli (E. coli) was studied to find the optimal sterilization conditions using electrostatic atomization with a near ultraviolet light-emitting diode (near UV-LED) and TiO₂ nanofiber films. Three types of near UV-LEDs of different wavelengths (365 nm, 375 nm, 385 nm) were used in this investigation. In order to enhance the LED performances, TiO₂ nanofiber films were utilized for the production of a photo-chemical catalytic effect. In these studies, the flow rate condition of the E. coli mixture was varied from 2 ml/h to 10 ml/h for the purposes of measuring the capabilities of the proposed sterilization method. During these electrostatic atomization experiments, Each LED irradiated a TiO₂ nanofiber film and atomized E. coli mixture. The results of these experiments were compared with electrostatic atomization performed without the use of photo-chemical catalyst effects. The experimental result shows that the optimal sterilization effect of E. coli is 375 nm wavelength with a TiO₂ nanofiber employed during electrostatic atomization.