Adsorption and breakdown of penicillin antibiotic in the presence of titanium oxide nanoparticles in water

The fate and transport of antibiotics in natural water systems is controlled in part by interactions with nanometer (10⁻⁹ m) metal oxide particles. Experiments were performed by mixing solutions of ampicillin (AMP), a common, penicillin-class human and veterinary antibiotic, with 25 nm-TiO₂ (anatase) nanoparticles at different pH conditions. Both sorption and degradation of AMP were observed in the AMP-nanoparticle solutions. For AMP concentrations from ∼3 μM to 2.9 mM the overall AMP removal from solution can be described by linear isotherms with removal coefficients (K_r) of 3028 (±267) L kg⁻¹ at pH 2, 11,533 (±823) L kg⁻¹ at pH 4, 12,712 (±672) L kg⁻¹ at pH 6, and 1941 (±342) L kg⁻¹ at pH 8. Mass spectral analysis of AMP solutions after removal of the solid nanoparticles yielded ions that indicate the presence of peniclloic acid, penilloic acid and related de-ammoniated by-products as possible compounds resulting from the degradation of AMP at the TiO₂ surface.     

Ecotoxicity of nanosized TiO2. Review of in vivo data

This report presents an exhaustive literature review of data on the effect of nanoparticulate TiO₂ on algae, higher plants, aquatic and terrestrial invertebrates and freshwater fish. The aim, to identify the biologically important characteristics of the nanoparticles that have most biological significance, was unsuccessful, no discernable correlation between primary particle size and toxic effect being apparent. Secondary particle size and particle surface area may be relevant to biological potential of nanoparticles, but insufficient confirmatory data exist. The nanotoxicity data from thirteen studies fail to reveal the characteristics actually responsible for their biological reactivity because reported nanotoxicity studies rarely carry information on the physicochemical characteristics of the nanoparticles tested. A number of practical measures are suggested which should support the generation of reliable QSAR models and so overcome this data inadequacy.     

Inactivation of LPS and RNase A on photocatalytically active surfaces

TiO₂ coated surfaces are able to generate highly reactive oxidizing species under mild UV-A light exposure in the presence of water and oxygen. We have demonstrated that these radicals are sufficient to eliminate different pathogenic bacteria, by breaking their cell walls. The photocatalytic activity of surfaces coated with titanium dioxide offers therefore an alternative possibility of disinfection. However, restriction of bacterial growth does not protect surfaces from bacterial derived contaminations, such as endotoxins. Lipopolysaccharides (LPS) and Ribonuclease A (RNAse A) represent the two most abundant contaminations, causing severe problems in biomedical and immunological research as well as in the pharmaceutical industry. Due to their high stability, complete removal of these contaminants is technically challenging. Using irradiated TiO₂ coated glass plates, RNAse A and LPS containing contaminations could be completely inactivated. By establishing highly sensitive immuno-based assays, destruction of the contaminants was quantified and shown to be independent of the initial concentrations, following a zero-order reaction. Exposure for 96 h resulted in a reduction of 11 ng of LPS and 7 units of RNase A cm⁻² surface. These amounts are comparable to contamination levels found under standard working conditions. Titanium dioxide coatings provide therefore a powerful tool for auto-disinfection and self-cleaning of surfaces.     

A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO₂NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO₂NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO₂NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO₂NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO₂NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO₂NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.     

光催化技术及其在室内空气净化方面研究现状

阐述了光催化技术的基本原理、二氧化钛光催化剂的特性,以及光催化技术在环境保护领域的广阔应用。介绍了中国室内空气污染的现状和甲醛、苯系物等主要污染物的性质与来源。简单讨论了物理法,化学法等主要的室内空气污染处理技术,突出表述了光催化技术的优势。从降解机理、降解效果、反应器应用等3个方面介绍了光催化技术在室内空气净化方面的研究现状。指出了单一技术的不足和联合协同作用的必要性。强调了将研究结果投入实际运用的迫切性,希望真正有效的室内空气净化器尽早普及。     

Gravity orientation in social wasp comb cells (Vespinae) and the possible role of embedded minerals

Social wasps and hornets maintain their nest in the dark. The building of the combs by all Vespinae is always in the direction of the gravitational force of Earth, and in each cell's ceiling, at least one 'keystone' is embedded and fastened by saliva. The sensory mechanisms that enable both building of sizeable symmetrical combs and nursing of the brood in the darkness merit investigation, and the aim of the present study was to identify and characterize the 'keystones' that exist in the ceiling and in the walls of the social wasp comb cells. Bio-ferrography was used to isolate magnetic particles on slides. These slides, as well as original cells, were analyzed in an environmental scanning electron microscope by a variety of analytical tools. It was found that both the roof and the walls of each comb cell bear minerals, like ferrites, as well as Ti and Zr. The latter two elements are less abundant in the soil around the nest. Ti and Zr are known to reflect infrared (IR) light. IR imaging showed a thermoregulatory center in the dorsal thorax of the adult Oriental hornet. It is not known yet whether these insects can sense IR light.     

天然麦饭石负载TiO2的光催化性能研究

采用溶胶-凝胶法制备了二氧化钛负载于天然麦饭石表面热处理后得到复合光催化剂TiO2/麦饭石,并通过N2吸附-脱附、XRD及IR对其进行表征。探讨了以天然麦饭石为载体制备具有较高光催化活性的负载型TiO2/天然麦饭石复合物的各种影响因素:焙烧温度,加投量,pH值等。研究结果表明:200℃焙烧条件下TiO2/麦饭石复合物具有最大的光催化活性,达到了纯TiO2的光催化效果:对罗丹明B脱色率随着光催化剂增多而增大;对罗丹明B在pH值7～9时具有最大的降解率,开拓和优化TiO2光催化效能的新途径。     

Effect of molecular properties on the photocatalytic degradation rates of dichlorophenols and dichloroanilines in aqueous TiO2 suspensions

The kinetics of the photocatalytic degradation of 10 different dichlorophenols and dichloroanilines have been investigated experimentally and theoretically. With the intention of finding certain molecular indices in order to determine the degradation rates of aromatic pollutants, geometry optimizations of the compounds have been performed with the semiempirical PM3 method. The molecular orbital calculations have been carried out by an SCF method using the RHF formalism. The correlations between the apparent first-order rate constants and the calculated molecular properties of the compounds have been examined. Four different structure–activity relationships have been developed expressing the logarithms of the rate constants in terms of the Hammett constants, electron densities of the substituents, the coefficients and the energies of the highest occupied molecular orbitals HOMO, and 1-octanol/water partition coefficients log?K _OW.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

Photocatalytic activity of titanium dioxide modified concrete materials – Influence of utilizing recycled glass cullets as aggregates

Combining the use of photocatalysts with cementitious materials is an important development in the field of photocatalytic air pollution mitigation. This paper presents the results of a systematic study on assessing the effectiveness of pollutant degradation by concrete surface layers that incorporate a photocatalytic material – Titanium Dioxide. The photocatalytic activity of the concrete samples was determined by photocatalytic oxidation of nitric oxide (NO) in the laboratory. Recycled glass cullets, derived from crushed waste beverage bottles, were used to replace sand in preparing the concrete surface layers. Factors, which may affect the pollutant removal performance of the concrete layers including glass color, aggregate size and curing age, were investigated. The results show a significant enhancement of the photocatalytic activity due to the use of glass cullets as aggregates in the concrete layers. The samples fabricated with clear glass cullets exhibited threefold NO removal efficiency compared to the samples fabricated with river sand. The light transmittance property of glass was postulated to account for the efficiency improvement, which was confirmed by a separate simulation study. But the influence of the size of glass cullets was not evident. In addition, the photocatalytic activity of concrete surface layers decreased with curing age, showing a loss of 20% photocatalytic activity after 56-day curing.