Oxidative degradation of 4‐nitrophenol in UV‐illuminated titania suspension

An internally‐irradiated annular photoreactor has been used to investigate the oxidative degradation of aqueous 4‐nitrophenol with titania as the photocatalyst. Reaction runs were performed over a 3‐h period and in practically all cases, complete degradation was possible within about 2 h. The kinetics was determined as a function of nitrophenol concentration, oxygen partial pressure, catalyst loading, pH, temperature and light intensity. The reaction was characterised by a relatively low activation energy of 7.83 kJ mol^?1 although transport intrusions were negligible. Rate decreased almost exponentially with pH while a quadratic (maximum) behaviour with respect to both oxygen pressure and nitrophenol concentration is symptomatic of self‐inhibition possibly due to the formation of intermediates which competitively adsorb on similar sites to the reactants. Increased catalyst dosage also improved the reaction rate although the possible effects of light scattering and solution opacity caused a drop at loadings higher than about 1.20 g dm^?3. Rate, however, has a linear dependency on light intensity, suggesting that hole–electron recombination processes were negligible at the conditions investigated. © 2001 Society of Chemical Industry     

Dynamic study of polystyrene-block-poly(4-vinylpyridine) copolymer in bulk and confined in cylindrical nanopores

AAO template is highly recommended to nanostructure polymers and to study polymer properties under confinement. The dynamic properties of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) under confinement using broadband dielectric spectroscopy are investigated in this work and the results compared to those of the bulk. Anodized aluminum oxide (AAO) membranes, having pore diameters from tens to hundreds of nanometers in size, were used to confine PS-b-P4VP. Moreover, the influence of gold nanoparticles (AuNPs) in the copolymer matrix was also studied. The morphology and structure of the bulk copolymer and the copolymer confined in the AAO templates were characterized by transmission electron microscopy, scanning electron microscopy and Small Angle X-Ray Scattering. For PS-b-P4VP in bulk, dielectric relaxation techniques allowed studying selectively the P4VP segmental dynamics within the diblock. At high temperature this copolymer presents a dominant peak (MWS relaxation), most likely originated by the relatively high conductivity combined with the presence of interfaces emerging in the nanostructured samples. Moreover, a pronounced β-relaxation is observed for the copolymer compared with that of pure P4VP. This is likely due to a non-negligible contribution from the α-relaxation of the PS component. The γ-relaxation is markedly different in the copolymer, which is evidenced by a distinct temperature dependence of the resulting relaxation times. When the copolymer is embedded in alumina nanopores with small pore diameters (25 and 35 nm) there are significant changes, where the tendency is going to a faster dynamics when the pore diameter decreases more likely related to the relevance of surface effects. The presence of the AuNPs in the system enhances this effect. These results are in agreement with segregated structures found in the block copolymer by TEM and SAXS.     

(6<Emphasis Type="Italic">R</Emphasis>, 10<Emphasis Type="Italic">R</Emphasis>)-6,10,14-Trimethylpentadecan-2-one,a Dominant and Behaviorally Active Component in Male Orchid Bee Fragrances

6,10,14-Trimethylpentadecan-2-one (Hexahydrofarnesyl acetone; HHA) previously has been found to be a major component in tibial fragrances of male orchid bees, Euglossa spp. HHA is a chiral molecule with four possible stereoisomers, (6R, 10R)-, (6R, 10S)-, (6S, 10R)-, and (6S, 10S)-6,10,14-trimethylpentadecan-2-one. In the present study, we characterized HHA extracted from Euglossa as the pure enantiomer (6R, 10R)-6,10,14-trimethylpentadecan-2-one. During bioassays in Mexico and Panama, the synthetic RR-isomer attracted males of six species of orchid bees, including three that were known to contain HHA in their tibial fragrances. Possible sources of HHA for wild bees are flowers of euglossophilous orchids and aroids. With a molecular weight of 268, HHA is the largest natural molecule known to attract male orchid bees in pure form. Its attractiveness to males suggests that low-volatility compounds have a function in male signals, e.g., serve as a “base note” in complex odor bouquets.     

Removal of heavy metals from kaolin using an upward electrokinetic soil remedial (UESR) technology

An upward electrokinetic soil remedial (UESR) technology was proposed to remove heavy metals from contaminated kaolin. Unlike conventional electrokinetic treatment that uses boreholes or trenches for horizontal migration of heavy metals, the UESR technology, applying vertical non-uniform electric fields, caused upward transportation of heavy metals to the top surface of the treated soil. The effects of current density, treatment duration, cell diameter, and different cathode chamber influent (distilled water or 0.01 M nitric acid) were studied. The removal efficiencies of heavy metals positively correlated to current density and treatment duration. Higher heavy metals removal efficiency was observed for the reactor cell with smaller diameter. A substantial amount of heavy metals was accumulated in the nearest to cathode 2 cm layer of kaolin when distilled water was continuously supplied to the cathode chamber. Heavy metals accumulated in this layer of kaolin can be easily excavated and disposed off. The main part of the removed heavy metals was dissolved in cathode chamber influent and moved away with cathode chamber effluent when 0.01 M nitric acid was used, instead of distilled water. Energy saving treatment by UESR technology with highest metal removal efficiencies was provided by two regimes: (1) by application of 0.01 M nitric acid as cathode chamber influent, cell diameter of 100 mm, duration of 18 days, and constant voltage of 3.5 V (19.7 k Wh/m(3) of kaolin) and (2) by application of 0.01 M nitric acid as cathode chamber influent, cell diameter of 100 cm, duration of 6 days, and constant current density of 0.191 mA/cm(2) (19.1 k Wh/m(3) of kaolin).     

Reflectivity spectra and colors of porous anodic aluminum oxide containing silver nanoparticles by plasmonic absorption

The reflectivity spectra and color of porous anodic aluminum oxide (AAO) nanostructures containing the assembly of silver (Ag) nanoparticles (NPs) with a diameter of -10 nm were investigated. The Ag NPs were assembled inside the pores of AAO with a diameter of -60 nm by dip-coating process during which Ag NPs adsorbed on the surface of AAO and driven inside the pores by capillary force upon the evaporation of solvent. The reflectivity spectra and associated colors of AAO with Ag NPs were determined by the plasmonic absorption of light by Ag NPs. Even with the monolayer coverage of Ag NPs in the pores of AAO, the reflectivity is significantly reduced specifically at -465 nm wavelength by a strong plasmonic absorption, resulting in its golden color. Aggregating Ag NPs by post-annealing at 300 and 400 degrees C changed the color to pink due to the red-shift of absorption. These results are indicative of potential color-engineering of NPs/AAO platform by wavelength-selective reduction of reflected light intensity and using it in direct optical read-out of change of surface and morphology conditions.     

Photovoltaic device performance of single-walled carbon nanotube and polyaniline films on n-Si: device structure analysis

In this paper, we explore the use of two organic materials that have been touted for use as photovoltaic (PV) materials: inherently conducting polymers (ICPs) and carbon nanotubes (CNTs). Due to these materials' attractive features, such as environmental stability and tunable electrical properties, our focus here is to evaluate the use of polyaniline (PANI) and single wall carbon nanotube (SWNT) films in heterojunction diode devices. The devices are characterized by electron microscopy (film morphology), current-voltage characteristics (photovoltaic behavior), and UV/visible/NIR spectroscopy (light absorption). We have found that both PANI and SWNT can be utilized as photovoltaic materials in a simple bilayer configuration with n-type Silicon: n-Si/PANI and n-Si/SWNT. It was our aim to determine how photovoltaic performance was affected utilizing both PANI and SWNT layers in multilayer devices: n-Si/PANI/SWNT and n-Si/SWNT/PANI. The short-circuit current density increased from 4.91 mA/cm(2) (n-Si/PANI) to 12.41 mA/cm(2) (n-Si/PANI/SWNT), while an increase in power conversion efficiency by ~91% was also observed. In the case of n-Si/SWNT/PANI and its corresponding device control (n-Si/SWNT), the short-circuit current density was decreased by an order of magnitude. The characteristics of the device were affected by the architecture and the findings have been attributed to the more effective transport of holes from the PANI to SWNT and less effective transport of holes from PANI to SWNT in the respective multilayer devices.     

Bioaccumulation, biotransformation, and metabolite formation of fipronil and chiral legacy pesticides in rainbow trout

To assess the fate of current-use pesticides, it is important to understand their bioaccumulation and biotransformation by aquatic biota. We examined the dietary accumulation and enantioselective biotransformation of the chiral current-use pesticide fipronil, along with a mixture of selected chiral [alpha-hexachlorocyclohexane (alpha-HCH), heptachlor epoxide (HEPX), polychlorinated biphenyls (PCBs) 84, 132, 174, o,p'-DDT, and o,p'-DDD] and nonchiral (p,p'-DDT, p,p'-DDD) organochlorine compounds in juvenile rainbow trout (Oncorhynchus mykiss). Fish rapidly accumulated all compounds, as measured in the carcass (whole body minus liver and GI tract) during the 32 d uptake phase, which was followed by varying elimination rates of the chemicals (half-lives (t1/2s) ranging from 0.6 d for fipronil to 77.0 d for PCB 174) during the 96 d depuration period. No biotransformation was observed for alpha-HCH, HEPX, PCB 174, o,p'-DDT, or o,p'-DDD based on consistent enantiomeric fractions (EFs) in the fish and their t1/2s falling on a log K(ow)--log t1/2 relationship established for recalcitrant contaminants in fish. p,p'-DDT and PCBs 84 and 132 were biotransformed based on the former's t1/2 position below the log K(ow)--log t1/2 relationship, and the PCBs change in EF. Fipronil was rapidly biotransformed, based on a change in EF, a t1/2 that fell below the log K(ow)--log t1//2 relationship, which accounted for 88% of its elimination, and the rapid formation of fipronil sulfone, a known metabolite. Fipronil sulfone was found to persist longer (t1/2 approximately 2 d) than its parent compound fipronil (t1/2 approximately 0.6 d) and needs to be considered in fate studies of fipronil. This research demonstrates the utilities of the log K(ow)--log t1/2 relationship as a mechanistic tool for quantifying biotransformation and of chiral analysis to measure biotransformation in fish.     

Use of cover crops in short rotation hardwood plantations to control erosion

This study was designed to test whether the cultivation of cover crops between tree rows in short-rotation woody crop (SRWC) plantations could reduce erosion. Sweetgum (Liquidambar styraciflua L.) seedlings were planted as the SRWC at a 1.5×3 m spacing. Four cover crops, annual ryegrass (Lolium multiflorum L. a winter annual grass); tall fescue (Festuca arundinacea L. a cool-season perennial grass); crimson clover (Trifolium incarnatum L. a winter annual legume); and Interstate sericea lespedeza [Lespedeza cuneata (Dumont) G. Don. a summer growing-perennial legume], were tested at two different strip widths (1.22 and 2.44 m) in comparison with complete competition control. Erosion was measured from 1 August, 1995 to 8 March, 1997 (585 days) by sediment accumulation near the fence where 72 PVC pipes were inserted into soil on a 4.65 m² (50 ft³) grid area of each plot. The total rainfall recorded during this period was 2422.91 mm (95.3 in.). All cover crops reduced erosion over the complete competition free plot (control), although tall fescue performed poorly at the narrow strip width. There were no significant differences between grasses and legumes for erosion control. Winter annual crops provided significantly more erosion protection than summer growing-perennials. With the exception of tall fescue, narrow strip widths performed as well as wider strip widths. The results indicate that cover crops ryegrass, crimson clover, lespedeza and tall fescue controlled about 64, 61, 51 and 37% soil erosion respectively as compared to the control during the critical early years of stand development in SRWC hardwood plantations.     

Nanocrystalline diamond film for biosensor applications

In this study, we have developed a novel capacitive biosensor based on interdigitated gold nanodiamond (GID-NCD) electrode for detection of C-reactive protein (CRP) antigen. CRP is one of the plasma proteins known as acute-phase proteins and its levels rise dramatically during inflammatory processes occurring in the body. It has been reported that CRP in serum can be used for risk assessment of cardiovascular diseases. The antibodies immobilization were confirmed by fourier transform spectroscopy (FTIR) and contact angle measurements. In this capacitive biosensor, nanocrystalline diamond acting as a dielectric layer between the electrodes. The CRP antigen detection was performed by capacitive/dielectric-constant measurements. Our results showed that the response of NCD-based capacitive-based biosensor for CRP antigen was dependent on both concentration (25–800 ng/ml) as well as frequency (50–350 MHz). Furthermore, using optimized conditions, the biosensors developed in this study can be potentially used for detection of elevated level of risk markers protein in suspected subjects for early diagnosis of disease.