Sensitized photooxygenation of mononitrophenols in micellar media

The singlet molecular oxygen‐mediated photooxidation of simple nitrophenols was studied in micellar (CTAB) alkaline solutions.

A different behaviour for the values of the overall rate constant (K_t ) and the reactive rate constant (K_t ) in the interaction nitrophenol‐singlet molecular oxygen was observed as a function of surfactant concentration. The former decreases as [CTAB] increases, from values of 1–3 × 10⁹ M^–1 s^–1 in the absence of surfactant to values at least one order of magnitude lower at [CTAB] ～0.1 M. Parallel, k_t remains practically unaffected, in values of the order of 10⁶ — 10⁷ M^–l s^–1, depending on the particular nitrophenol, within the same [CTAB] range. The quantum yield of nitrophenols photooxidation reaches a maximum at [CTAB] ～0.1 M.

The results are discussed in terms of a combination of causes, the polarity of the nitrophenolic microenvironment being the driving effect. The implication of the results on environmental decontamination are also analyzed.     

Simple synthesis of hydrazones with quorum quenching activity at room temperature in water

Environmental Chemistry Letters - The hydrazone moiety is a major function in medicinal chemistry because of its wide range of pharmacological applications. Actual synthetic procedures usually...     

Synthesis of quinoxalines using Gum Arabic as a nontoxic metal-free biocatalyst at room temperature in aqueous media

Environmental Chemistry Letters - In the present study, Gum Arabic was used as a metal-free biocatalyst in the synthesis of quinoxaline derivatives through condensation of 1,2-diamines and...     

Analysis of polycyclic aromatic hydrocarbons by sensitized room temperature phosphorescence

Direct and selective simultaneous determination of several polycyclic aromatic hydrocarbons by sensitized room temperature phosphorescence in sodium dodecylsulphate micellar solutions was studied. This approach improved, for example, the selectivity factor in determining pyrene in the presence of fluoranthene by a factor of 350, and determined benz[a]anthracene and anthracene in the presence of pyrene with the selectivity factors as high as 200–220. Triphaflavine and acridine orange as triplet energy donors, thallium (I) nitrate as a heavy atom, and sodium sulphite were used as scavengers of oxygen. A comparative study of linear concentration ranges, detection limits and selectivity factors is presented here for pyrene, benz[a]anthracene and anthracene determination by fluorescence, phosphorescence and sensitized phosphorescence. Electronic Publication     

Synthesis of 3-carboxycoumarins at room temperature in water extract of banana peels

The 3-carboxycoumarin is a major heterocycle in many biologically active agents, including anti-cancer, antibacterial and cosmetics. 3-Carboxycoumarins are also involved in the actions of plant growth hormones and growth regulators. Many catalytic systems have been used for the synthesis of 3-carboxycoumarins but such systems present issues such as harsh reaction conditions, tedious work-up and use of toxic solvents. Therefore, here we tested the synthesis of 3-carboxycoumarins by one-pot Knoevenagel condensation and intramolecular cyclization of various 2-hydroxybenzaldehydes with meldrum’s acid, using water extract of banana. Products were obtained in 76–94% yields in 420–490 min at room temperature by simple filtration.     

Preparation,characterization of sludge adsorbent and investigations on its removal of hydrogen sulfide under room temperature

To recycle the sludge resource from sewage treatment plants and solve the problem of odor pollution, the sludge was converted into an adsorbent by carbonized pyrolysis and the process was optimized by orthogonal experiments. The capability for odor removal as well as the structure of the adsorbent was studied with H₂S as a target pollutant. The results indicate that the main factor affecting the deodorization performance of the adsorbent is the activating time. The sludge adsorbent sample SAC1 prepared under optimum conditions exhibits the best deodorization performance with a H₂S breakthrough time of 58 min and an iodine value nearly that of the coal activated carbon. The breakthrough time of H₂S is much longer than that on the coal activated carbon. On the other hand, characterization results from X-ray diffractometer (XRD), X-ray photoelectron spectrometer (XPS) and scanning electron microscope (SEM) techniques show that SAC1 is composed of mainly graphite carbon with lower oxygen content on the surface. The bulk of SAC1 exhibits a honeycomb structure with well developed porosity and a high specific surface area of 120.47 m²·g^-1, with the average pore diameter being about 5 nm. Such a structure is in favor of H₂S adsorption. Moreover, SAC1 is detected to contain various metal elements such as Zn, Fe, Mg, etc., leading to a superior deodorization property to that of coal activated carbon.     

Robust photo-assisted removal of NO at room temperature:Experimental and density functional theory calculation with optical carrier

Photo-assisted SCR(PSCR) offers a potential solution for removal of NO at room temperature. MnTiO_x as PSCR catalyst exhibits superior performance with NO removal of 100% at the room temperature. Electron paramagnetic resonance(EPR) analysis revealed the presence of numerous oxygen vacancies on MnTiO_x. Optical carrier density functional theory(DFT) calculations showed that the threedimensional orbital hybridization of Mn and Ti is significantly enhanced under light irradiati...     

Introducing effects of temperature and CO2 elevation on tree growth into a statistical growth and yield model

Impacts of elevated temperature and CO₂ on tree growth were introduced into a statistical growth and yield model for Finnish conditions based on corresponding predictions obtained from a physiological growth model. This one-way link between models was made by means of species-specific transfer functions describing the increase in stem volume growth of trees as a function of elevated temperature and CO₂, stand density and the tree's competition status in a stand of Scots pine (Pinus sylvestris), silver birch (Betula pendula) and Norway spruce (Picea abies). This method allows the inner dynamics of the statistical model to be followed when the impacts of temperature and CO₂ elevation on tree growth are introduced into the calculation of volume growth and further allocated between diameter and height growth. In this way compatibility with previous predictions of tree growth by means of statistical models and related model systems under current climatic conditions could be retained.The performance of the statistical model with species-specific transfer functions was evaluated by comparing its predictions with corresponding predictions given by a physiological model under conditions of elevated temperature and CO₂. These calculations revealed that the growth response of individual trees to elevated temperature and CO₂ can be introduced into the statistical model from a physiological growth model with an outcome that results in fairly satisfactory growth responses at the stand level as well.     

Room temperature synthesis of 2H-1,4-benzoxazine derivatives using a recoverable ionic liquid medium

2H-1,4-Benzoxazines are major heterocyclic compounds with interesting biological and synthetic applications. Therefore, it would be very interesting to develop new efficient methods for their synthesis. Here, we synthesized 2H-1,4-benzoxazines in one pot using K₂CO₃/H₂O in the ionic liquid of choice, [omim][BF₄]. After reactions, products are extracted from [omim][BF₄] by Et₂O and the ionic liquid is recovered and successfully reused over several recycles. Results show that high yields of 3-aryl-2H-1,4-benzoxazine derivatives are obtained chemoselectively at room temperature from their corresponding o-aminophenols and phenacyl bromides. To our knowledge, our method represents the most efficient and straightforward route for the synthesis of 3-aryl-2H-1,4-benzoxazine derivatives in short times and under environmentally benign conditions.     

Effect of hydrostatic pressure and temperature on the activity and synthesis of chitinases of Antarctic Ocean bacteria

The formation of chitinases by psychrophilic and psychrotrophic marine Antarctic bacteria and the activity of these extracellular enzymes were investigated under simulated deep-sea conditions. The formation of the chitinases was affected by hydrostatic pressure of 400 bars. However, the extent of pressure inhibition differed with the bacterial strains tested and was considerably less with the extreme psychrophilic bacteria isolated from sediments of greater depth. Growth of these psychrophilic strains had a moderately barophilic character at 400 bars, whereas growth of the psychrotrophic strains was clearly restricted under simulated deep-sea conditions. With regard to the activity of the extracellular chitinases of various bacterial strains, a relatively uniform response was found. All chitinases were highly barotolerant at near neutral pH and were active up to 1000 bars. Low temperatures reduced their activity but not their barotolerance. A low pH of 5.1 diminished the barotolerance of some chitinases. The results suggest that the indigenous deep-sea bacteria are capable of decomposing chitin settled to or produced in the depth of the Antarctic Ocean.     

Coexistence of the niche and neutral perspectives in community ecology

The neutral theory for community structure and biodiversity is dependent on the assumption that species are equivalent to each other in all important ecological respects. We explore what this concept of equivalence means in ecological communities, how such species may arise evolutionarily, and how the possibility of ecological equivalents relates to previous ideas about niche differentiation. We also show that the co-occurrence of ecologically similar or equivalent species is not incompatible with niche theory as has been supposed, because niche relations can sometimes favor coexistence of similar species. We argue that both evolutionary and ecological processes operate to promote the introduction and to sustain the persistence of ecologically similar and in many cases nearly equivalent species embedded in highly structured food webs. Future work should focus on synthesizing niche and neutral perspectives rather than dichotomously debating whether neutral or niche models provide better explanations for community structure and biodiversity.     

Phototransformation of fibrate drugs in aqueous media

The photochemical conversion of bezafibrate, gemfibrozil, fenofibrate and fenofibric acid has been examined in aqueous media. Irradiation with a solar simulator in distilled water caused about 10% degradation for the first three drugs after 200 hr, while fenofibric acid was completely degraded after 100 hr. Experiments have also been performed in the presence of nitrates or humic acids, considered as environmental photosensitizers, and only for gemfibrozil a reduction of degradation has been observed. Photoproducts have been characterized and the mechanistic pathways discussed on the basis of experimental and literature data.     

Longitudinal monitoring of neutral and adaptive genomic diversity in a reintroduction

Restoration programs in the form of ex-situ breeding combined with reintroductions are becoming critical to counteract demographic declines and species losses. Such programs are increasingly using genetic management to improve conservation outcomes. However, the lack of long-term monitoring of genetic indicators following reintroduction prevents assessments of the trajectory and persistence of reintroduced populations. We carried out an extensive monitoring program in the wild for a threatened small-bodied fish (southern pygmy perch, Nannoperca australis) to assess the long-term genomic effects of its captive breeding and reintroduction. The species was rescued prior to its extirpation from the terminal lakes of Australia's Murray-Darling Basin, and then used for genetically informed captive breeding and reintroductions. Subsequent annual or biannual monitoring of abundance, fitness, and occupancy over a period of 11 years, combined with postreintroduction genetic sampling, revealed survival and recruitment of reintroduced fish. Genomic analyses based on data from the original wild rescued, captive born, and reintroduced cohorts revealed low inbreeding and strong maintenance of neutral and candidate adaptive genomic diversity across multiple generations. An increasing trend in the effective population size of the reintroduced population was consistent with field monitoring data in demonstrating successful re-establishment of the species. This provides a rare empirical example that the adaptive potential of a locally extinct population can be maintained during genetically informed ex-situ conservation breeding and reintroduction into the wild. Strategies to improve biodiversity restoration via ex-situ conservation should include genetic-based captive breeding and longitudinal monitoring of standing genomic variation in reintroduced populations.     

Unexpected removal of the most neutral cationic pharmaceutical in river waters

Contamination of surface waters by pharmaceuticals is now widespread. There are few data on their environmental behaviour, particularly for those which are cationic at typical surface water pH. As the external surfaces of bacterio-plankton cells are hydrophilic with a net negative charge, it was anticipated that bacterio-plankton in surface-waters would preferentially remove the most extensively-ionised cation at a given pH. To test this hypothesis, the persistence of four, widely-used, cationic pharmaceuticals, chloroquine, quinine, fluphenazine and levamisole, was assessed in batch microcosms, comprising water and bacterio-plankton, to which pharmaceuticals were added and incubated for 21 days. Results show that levamisole concentrations decreased by 19 % in microcosms containing bacterio-plankton, and by 13 % in a parallel microcosm containing tripeptide as a priming agent. In contrast to levamisole, concentrations of quinine, chloroquine and fluphenazine were unchanged over 21 days in microcosms containing bacterio-plankton. At the river-water pH, levamisole is 28 % cationic, while quinine is 91–98 % cationic, chloroquine 99 % cationic and fluphenazine 72–86 % cationic. Thus, the most neutral compound, levamisole, showed greatest removal, contradicting the expected bacterio-plankton preference for ionised molecules. However, levamisole was the most hydrophilic molecule, based on its octanol–water solubility coefficient (K _ow). Overall, the pattern of pharmaceutical behaviour within the incubations did not reflect the relative hydrophilicity of the pharmaceuticals predicted by the octanol–water distribution coefficient, D _ow, suggesting that improved predictive power, with respect to modelling bioaccumulation, may be needed to develop robust environmental risk assessments for cationic pharmaceuticals.     

Catalytic activities and mechanism of formaldehyde oxidation over gold supported on MnO<Subscript>2</Subscript> microsphere catalysts at room temperature

MnO₂ microspheres with various surface structures were prepared using the hydrothermal method, and Au/MnO₂ catalysts were synthesized using the sol-gel method. We obtained three MnO₂ microspheres and Au/MnO₂ samples: coherent solid spheres covered with wire-like nanostructures, solid spheres with nanosheets, and hierarchical hollow microspheres with nanoplatelets and nanorods. We investigated the properties and catalytic activities of formaldehyde oxidation at room temperature. Crystalline structures of MnO₂ are the main factor affecting the catalytic activities of these samples, and γ-MnO₂ shows high catalytic performance. The excellent redox properties are responsible for the catalytic ability of γ-MnO₂. The gold-supported interaction can change the redox properties of catalysts and accelerate surface oxygen species transition, which can account for the catalytic activity enhancement of Au/MnO₂. We also studied intermediate species. The dioxymethylene (DOM) and formate species formed on the catalyst surface were considered intermediates, and were ultimately transformed into hydrocarbonate and carbonate and then decomposed into CO₂. A proposed mechanism of formaldehyde oxidation over Au/MnO₂ catalysts was also obtained.     

Real-time monitoring of nanoparticle retention in porous media

Nanoparticles are not specifically targeted in conventional treatment schemes; consequently, typical wastewater treatment systems are ineffective for nanoparticles removal. With rapidly increasing concern over their health effects, improved understanding of nanoparticle transport and retention in porous media filters is critical because of its application in new wastewater treatment methods and for assessment of the fate of the discharged nanoparticles in soil. In this study, a unique and robust integrated method is developed and validated. Experimentally, this approach uses an on-line, real-time, and in situ method for measuring nanoparticle retention dynamics, eliminating the laborious and less accurate sampling and off-line analysis. The data analysis part is a process simulator which provides both kinetic properties of the retention process as well as the overall capacity and loading. This technique is validated by application to the transport and retention of TiO₂ nanoparticles in two vastly different porous filtration media—activated carbon and sand. TiO₂ retained concentrations ranged from 0.24 to 0.37 mg g^?1 for activated carbon and 0.01–0.014 mg g^?1 for sand. The integrated method presented here is useful for both comparison of the filtration effectiveness of various porous materials as well as for process optimization and scale-up for industrial applications.