An innovative pilot plant based on UVB and TiO2 (Anatase) allowed for photocatalytic degradation of organic micro-pollutants. The catalyst was immobilized onto a channel through which the solution containing a target molecule (methylene blue, MB) was re-circulated. Due to the cationic nature of the MB substrate, the adsorption reaction onto the catalyst surface provided a significant contribution to the overall degradation mechanism due to the negatively charged surface at neutral pH (TiO2 pHzpc = 6.8). The influence of the initial MB concentration was investigated in the range 0.3–2.0 mg L?1 with the Langmuir–Hinshelwood (LH) model showing good data correlations at concentrations up to 0.7 mg L?1, whereas at higher concentrations a pure zero-order (catalytic) kinetic trend was observed. Flow rate of the re-circulating solution sensibly influenced kinetics after the larger volumes of liquid exposed to UVB/TiO2 and to the better oxygen saturation in the liquid phase. UV?vis and HPLC-MS/MS experimental determinations allowed for identification of MB residual concentration and by-products. 相似文献
Summary: Organic‐inorganic nanocomposite hybrid coatings were prepared through a dual‐cure process involving cationic photopolymerization of a hyperbranched epoxy functionalized resin and subsequent condensation of an alkoxysilane inorganic precursor. All the formulations investigated gave rise to photocured films characterized by high gel content values. An increase in glass transition temperature and an increase in storage modulus above Tg in the rubbery plateau is observed with increasing TEOS content in the photocurable formulation. The important role of GPTS on reducing the inorganic domain size and avoiding macroscopic phase separation was demonstrated by TEM analyses.
TEM obtained for one of the cured films in the presence of GPTS. 相似文献
This review traces the development of addition-fragmentation chain transfer agents and related ring-opening monomers highlighting recent innovation in these areas. The major part of this review deals with reagents that give reversible addition-fragmentation chain transfer (RAFT). These reagents include dithioesters, trithiocarbonates, dithiocarbamates and xanthates. The RAFT process is a versatile method for conferring living characteristics on radical polymerizations providing unprecedented control over molecular weight, molecular weight distribution, composition and architecture. It is suitable for most monomers polymerizable by radical polymerization and is robust under a wide range of reaction conditions. It provides a route to functional polymers, cyclopolymers, gradient copolymers, block polymers and star polymers. 相似文献
Radical polymerization is one of the most widely used processes for the commercial production of high-molecular-weight polymers. The main factors responsible for the preeminent position of radical polymerization are the ability to polymerize a wide array of monomers, tolerance of unprotected functionality in monomer and solvent, and compatibility with a variety of reaction conditions. Radical polymerization is simple to implement and inexpensive in relation to competitive technologies. However, conventional radical polymerization severely limits the degree of control that researchers can assert over molecular-weight distribution, copolymer composition, and macromolecular architecture. This Account focuses on nitroxide-mediated polymerization (NMP) and polymerization with reversible addition-fragmentation chain transfer (RAFT), two of the more successful approaches for controlling radical polymerization. These processes illustrate two distinct mechanisms for conferring living characteristics on radical polymerization: reversible deactivation (in NMP) and reversible or degenerate chain transfer (in RAFT). We devised NMP in the early 1980s and have exploited this method extensively for the synthesis of styrenic and acrylic polymers. The technique has undergone significant evolution since that time. New nitroxides have led to faster polymerization rates at lower temperatures. However, NMP is only applicable to a restricted range of monomers. RAFT was also developed at CSIRO and has proven both more robust and more versatile. It is applicable to the majority of monomers subject to radical polymerization, but the success of the polymerization depends upon the selection of the RAFT agent for the monomers and reaction conditions. We and other groups have proposed guidelines for selection, and the polymerization of most monomers can be well-controlled to provide minimal retardation and a high fraction of living chains by using one of just two RAFT agents. For example, a tertiary cyanoalkyl trithiocarbonate is suited to (meth)acrylate, (meth)acrylamide, and styrenic monomers, while a cyanomethyl xanthate or dithiocarbamate works with vinyl monomers, such as vinyl acetate or N-vinylpyrrolidone. With the appropriate choice of reagents and polymerization conditions, these reactions possess most of the attributes of living polymerization. We have used these methods in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, including microgels and polymer brushes. Applications of these polymers include novel surfactants, dispersants, coatings and adhesives, biomaterials, membranes, drug-delivery media, electroactive materials, and other nanomaterials. 相似文献
The oxidation of nitrite and nitrous acid to *NO2 upon irradiation of dissolved Fe(III), ferric (hydr)oxides, and nitrate has previously been shown to enhance phenol nitration. This allowed the proposal of a new role for nitrite and nitrous acid in natural waters and atmospheric aerosols. This paper deals with the interaction between hydrogen peroxide, a key environmental factor in atmospheric oxidative chemistry, and nitrite/nitrous acid. The reaction between nitrous acid and hydrogen peroxide yields peroxynitrous acid, a powerful nitrating agent and an important intermediate in atmospheric chemistry. The kinetics of this reaction is compatible with a rate-determining step involving either H3O2+ and HNO2 or H2O2 and protonated nitrous acid. In the former case the rate constant between the two species would be 179.6 +/- 1.4 M(-1) s(-1), in the latter case it would be as high as (1.68 +/- 0.01) x 10(10) M(-1) s(-1) (diffusion-controlled reaction). Due to the more reasonable value of the rate constant, the reaction between H3O2+ and HNO2 seems more likely. In the presence of HNO2 + H2O2 the nitration of phenol is strongly enhanced when compared with HNO2 alone. The nitration rate of phenol in the presence of peroxynitrous acid decreases as pH increases, thus HOONO is a potential source of atmospheric nitroaromatic compounds in acidic water droplets. The mixture Fe(II) + H2O2 (Fenton reagent) can oxidize nitrite and nitrous acid to nitrogen dioxide, which results in phenol nitration. The nitration in the presence of Fe(II) + H2O2 + NO2-/HNO2 occurs more rapidly than the one with H2O2 + NO2-/HNO2 at pH 5, where little HNO2 is available to directly react with hydrogen peroxide. Both systems, however, are more effective than NO2-/HNO2 alone in producing nitrophenols from phenol. Another process leading to the oxidation of nitrite to nitrogen dioxide is the photo-Fenton one. It can be relevant at pH > or = 6, as nitrite does not react with H2O2 at room temperature. Under such conditions the source of Fe(II) is the photolysis of ferric (hydr)oxides (heterogeneous photo-Fenton reaction). In the presence of nitrite this reaction induces very effective nitrophenol formation from phenol. 相似文献
Egg parasitoids are able to find their hosts by exploiting their chemical footprints as host location cues. In nature, the
apolar epicuticular wax layer of plants that consists of several classes of hydrocarbons serves as the substrate that retains
these contact kairomones. However, experiments on chemical footprints generally have used filter paper as substrate to study
insect behavior. Here, we explored the ability of Trissolcus basalis (Scelionidae) females to discriminate between footprint cues left by male and female Nezara viridula (Pentatomidae) on leaves of their host plant Brassica oleracea (broccoli). Furthermore, we analyzed the chemical composition of the outermost wax layer of broccoli leaves to evaluate the
degree of overlap in insect and plant cuticular hydrocarbons that could lead to masking effects in the detection of footprint
cues. Our results showed that B. oleracea epicuticular wax retains the chemical footprints of adult bugs and allows T. basalis females to differentiate hosts of different sex. Traces of female bugs elicited more extensive searching behavior in egg
parasitoids than traces of males. The application of n-nonadecane, a compound specific to male N. viridula, on the tarsi of female bugs prevented parasitoid females from distinguishing between host male and host female footprints.
Analyses of B. oleracea leaves revealed that epicuticular waxes were mainly composed of linear alkanes, ketones, and secondary alcohols. Alkanes
were dominated by n-nonacosane (nC29) and n-hentriacontane (nC31), while male-specific n-nonadecane (nC19) was absent. The ecological significance of these results for parasitoid host location behavior is discussed. 相似文献
The effect of the combustion mode on particle emission was analyzed both in the cylinder and at the exhaust of a direct injection (DI) Common Rail (CR) transparent research diesel engine by means of spectroscopic and conventional methods. The engine was equipped with a flexible electronic control unit (ECU) capable of operating up to 5 injections per cycle with different start of injection and dwell time allowing performing different combustion modes. The conventional diesel combustion, the homogeneous charge compression ignition (HCCI), and the low temperature combustion (LTC) modes were analyzed. In-cylinder broadband UV–visible scattering and extinction measurements were carried out to follow the particle formation and oxidation processes as well as to have information about their chemical nature and size distribution. The characterization of the particulate emission at the exhaust was performed by means of an electrical low pressure impactor (ELPI), for the counting and the sizing of the particles, and an opacimeter, for measuring the smoke opacity. The in-cylinder measurements highlighted that particles ranged from 3 to 100 nm whatever was the combustion mode. Nevertheless, particles produced by a conventional diesel combustion process principally consist of soot. Whereas particles formed during HCCI and LTC modes are composed mainly of organic compounds. The exhaust particle emissions depend on the combustion mode both in terms of size and number. A larger amount of particles smaller than 100 nm was emitted during HCCI and LTC modes with respect to the conventional one. Moreover, HCCI mode showed a strong accumulation mode. Copyright 2012 American Association for Aerosol Research 相似文献