Control of Two-Photon Absorption in Organic Compounds by Pulse Shaping: Spectral Dependence

In this work, we investigate the control of the two-photon absorption process of a series of organic compounds via spectral phase modulation of the excitation pulse. We analyzed the effect of the pulse central wavelength on the control of the two-photon absorption process for each compound. Depending on the molecules` two-photon absorption position relative to the excitation pulse wavelength, different levels of coherent control were observed. By simulating the two-photon transition probability in molecular systems, taking into account the band structure and its positions, we could explain the experimental results trends. We observed that the intrapulse coherent interference plays an important role in the nonlinear process control besides just the pulse intensity modulation.

Single-wall carbon nanotubes modified with organic dyes: Synthesis, characterization and potential cytotoxic effects

This work deals with the covalent functionalization of single-wall carbon nanotubes (SWNTs) with phenosafranine (PS) and Nile Blue (NB) dyes. These dyes can act as photosensitizers in energy and electron transfer reactions, with a potential to be applied in photodynamic therapy. Several changes in the characteristic Raman vibrational features of the dyes suggest that a covalent modification of the nanotubes with the organic dyes occurs. Specifically, the vibrational modes assigned to the NH(2) moieties of the dyes are seen to disappear in the SWNT-dye nanocomposites, corroborating the bond formation between amine groups in the dyes and carboxyl groups in the oxidized nanotubes. The X-ray absorption (XANES) data also show, that the intense band at 398.6 eV attributed to 1s -> 2p pi* transition of the nitrogen of the aromatic PS ring, is shifted due to the bonding with the carbonic structure of the SWNTs. The cytotoxicity data of dyes-modified SWNT composites in the presence and absence of light shows that the SWNT-NB (4 mu g/mL) composite presents a good photodynamic effect, namely a low toxicity in the dark, higher toxicity in the presence of light and also a reduced dye photobleaching by auto-oxidation. (C) 2010 Elsevier B.V. All rights reserved.

Simple Method to Evaluate and to Predict Flash Points of Organic Compounds

Flash points (T(FP)) of organic compounds are calculated from their flash point numbers, N(FP), with the relationship T(FP) = 23.369N(FP)(2/3) + 20.010N(FP)(1/3) + 31.901. In turn, the N(FP) values can be predicted from boiling point numbers (Y(BP)) and functional group counts with the equation N(FP) = 0.974Y(BP) + Sigma(i)n(i)G(i) + 0.095 where G(i) is a functional group-specific contribution to the value of N(FP) and n(i) is the number of such functional groups in the structure. For a data set consisting of 1000 diverse organic compounds, the average absolute deviation between reported and predicted flash points was less than 2.5 K.

Experimental study of the degradation of volatile organic compounds by photocatalytic oxidation using TiO2 pellets

A fixed bed photocatalytic reactor has been designed and built with a UV
radiation source. Ti02 pellets were placed on the three fixed beds within the
reactor. Acetone was used as an indicator of volatile organic compounds (VOCs) during the experiment. Under the flow rate of 12.75 l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranged from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency; the obtained oxidation efficiency was in the range of 40-70% for various concentrations of untreated gases.

Coagulation and nano-filtration: a hybrid system for the removal of lower molecular weight organic compounds (LMWOC)

The removal of lower molecular weight organic compounds (LMWOC) from water is of increasing concern. While, nano-fi ltration (NF) is a good option, it removes only a fraction of the LMWOC. In this paper, NF experiments were conducted to remove oxalic acid and diuron in combination with coagulation using poly-aluminum chloride (PAC) as the coagulant. The results showed that this hybrid treatment system was effective in removing oxalic acid where almost a 100% removal effi ciency of oxalic acid was achieved. However, using PAC as coagulant to remove diuron from water was not effective. In order to improve the removal efficiency of diuron, 0.02 M NaCl was added to diuron and a 40% increase in the removal of diuron was achieved. Higher removal of diuron was achieved when the solution was treated with reverse osmosis (RO) when compared to the nano-filtration.

Effect of natural organic compounds on the removal of organic carbon in coagulation and flocculation processes

Natural organic matter (NOM) in water contains organic compounds that are both hydrophobic and hydrophilic with a wide range of molecular weights. It is composed of non-homogeneous organic compounds such as humic substances, amino acids, sugars, aliphatic and aromatic acids, and other chemical synthetic organic matters. NOM in water is a major concern not only because of its contribution to the formation of disinfection by-products (DBPs) and taste and odor, but also its influence on the demand for coagulants and disinfectants, the removal efficiency of water treatment processes, etc. This research aims at identifying the influence of NOM in coagulation and flocculation processes in order to optimize the coagulation and flocculation conditions. In this study, pretreated pond water was used as the source water. It was observed from the experimental results that: (1) The optimum pH for coagulation to remove NOM is around 7. (2) The optimum alum dose at this pH can vary from 125-1,225 mgl-1 when the TOC is increased from 4 to 25 mgl-1. (3) The presence of secondary compounds such as Ca2+, Mg2+ divalent cations had no significant effect on the removal of organic matter. (4) The presence of clay increased the organic removal by 15%. (5) The organic compound with higher molecular weight has higher removal affinity in coagulation process. (6) Floc size and settling velocity of floc and sludge production all increased with the increase in NOM concentration. From the results of Capillary Suction Time (CST) tests, the floc formed with lower TOC readily released the water to make the dewatering process easier. (7) The organic removal efficiency was significantly different for natural water containing non-homogeneous organic compounds compared to the synthetic water containing humic acid only (homogeneous organic matter). For example, the NOM removal efficiency was 80% for the synthetic water containing humic acid with TOC of 7 mgl-1 at pH 7; but the NOM removal for the pretreated pond water was 60%.

Organic compounds present in the natural Amazonian aerosol : characterization by gas chromatography–mass spectrometry

[1] As part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia (LBA)-Cooperative LBA Airborne Regional Experiment (CLAIRE) 2001 campaign in July 2001, separate day and nighttime aerosol samples were collected at a ground-based site in Amazonia, Brazil, in order to examine the composition and temporal variability of the natural “background” aerosol. We used a high-volume sampler to separate the aerosol into fine (aerodynamic diameter, AD < 2.5 μm) and coarse (AD > 2.5 μm) size fractions and quantified a range of organic compounds in methanolic extracts of the samples by a gas chromatographic-mass spectrometric technique. The carbon fraction of the compounds could account for an average of 7% of the organic carbon (OC) in both the fine and coarse aerosol fractions. We observed the highest concentrations of sugars, sugar alcohols, and fatty acids in the coarse aerosol samples, which suggests that these compounds are associated with primary biological aerosol particles (PBAP) observed in the forest atmosphere. Of these, trehalose, mannitol, arabitol, and the fatty acids were found to be more prevalent at night, coinciding with a nocturnal increase in PBAP in the 2–10 μm size range (predominantly yeasts and other small fungal spores). In contrast, glucose, fructose, and sucrose showed persistently higher daytime concentrations, coinciding with a daytime increase in large fungal spores, fern spores, pollen grains, and, to a lesser extent, plant fragments (generally >20 μm in diameter), probably driven by lowered relative humidity and enhanced wind speeds/convective activity during the day. For the fine aerosol samples a series of dicarboxylic and hydroxyacids were detected with persistently higher daytime concentrations, suggesting that photochemical production of a secondary organic aerosol from biogenic volatile organic compounds may have made a significant contribution to the fine aerosol. Anhydrosugars (levoglucosan, mannosan, galactosan), which are specific tracers for biomass burning, were detected only at low levels in the fine aerosol samples. On the basis of the levoglucosan-to-OC emission ratio measured for biomass burning aerosol, we estimate that an average of ∼16% of the OC in the fine aerosol was due to biomass burning during CLAIRE 2001, indicating that the major fraction was associated with biogenic particles.

Nanorods of vanadium compounds: synthesis, characterisation, and application in electrochemical energy storage

The synthesis and characterisation of nanorods of vanadium pentoxide, V(2)O(5), vanadium trioxide, V(2)O(3), vanadium dioxide, VO(2)(B), and vanadium nitride, VN, are presented, and their application in electrochemical supercapacitors and lithium-ion batteries is outlined. Specifically, a novel method for the preparation of V(2)O(5) nanorods is discussed. It involves ball milling as a first step and controlled annealing as a second step. Nanorods of V(2)O(5) can be converted into those of other vanadium-related phases by simple chemical reduction treatments. Such chemical transformations are pseudomorphic and often topotactic, that is, the resulting nanorods belong to a different chemical phase but tend to retain the original morphology and preferential crystal orientation dictated by parent V(2)O(5) crystals.

The corresponding properties of nanorods for their prospective application in electrochemical energy storage (lithium-ion batteries and electrochemical supercapacitors) are discussed. The synthesised V(2)O(5) nanorods possess a stable cyclic behaviour when they are used in a cathode of a lithium-ion battery and are suitable for use in an anode. VN nanorods synthesised by NH(3) reduction of V(2)O(5) were found to possess pseudocapacitive properties in aqueous electrolytes.

Electrochemical and quantum chemical assessment of two organic compounds from pyridine derivatives as corrosion inhibitors for mild steel in HCl solution under stagnant condition and hydrodynamic flow

 In this study, the inhibitive performance of two pyridine derivatives as corrosion inhibitors for mild steel was examined under stagnant condition and hydrodynamic flow in HCl solution at 25. °C. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were employed. To explore the inhibitors adsorption mechanism, Langmuir isotherm and quantum chemical studies were used. The results of electrochemical measurements show that the inhibitor concentration has a positive effect on its efficiency while for hydrodynamic condition, it is vice versa. Corrosion attack morphologies were observed at stagnant and hydrodynamic conditions to verify qualitatively the results obtained by electrochemical methods. © 2013 Elsevier Ltd.

Organic compounds from plant extracts and their effect on soil phosphorus availability

O objetivo deste trabalho foi avaliar o efeito de compostos orgânicos de extratos de plantas de seis espécies e da fertilização fosfatada na disponibilidade de fósforo no solo. Tubos de 30 cm de altura e 5 cm de diâmetro foram preenchidos com Latossolo Vermelho-Amarelo. Cada tubo constituiu uma parcela, em delineamento completamente casualizado, em arranjo fatorial 7x2, com quatro repetições. Extratos líquidos de aveia-preta (Avena strigosa), nabo forrageiro (Raphanus sativus), milho (Zea mays), milheto (Pennisetum glaucum), soja (Glycine max), sorgo forrageiro (Sorghum bicolor) e água (testemunha) foram aplicados em cada parcela, com ou sem fertilização com fosfato solúvel. Após sete dias de incubação, amostras de solo foram coletadas em várias profundidades, e foram analisadas as formas lábil, moderadamente lábil e não lábil de fósforo no solo. Houve acúmulo de fósforo inorgânico nas frações lábil e moderadamente lábil do solo, como conseqüência da adição dos extratos de plantas, principalmente na camada superficial (0-5 cm). O nabo forrageiro, com maior concentração de ácido málico e maior conteúdo de P no tecido do que outras espécies, foi o mais eficiente em incrementar a disponibilidade de P no solo.

Detection of volatile organic compounds using a polythiophene derivative

Conjugated polymers have been subject of great interest in the recent literature from both fundamental point of view and applied science perspective. Among the several types of conjugated polymers used in recent investigations, polythiophene and its derivatives have attracted considerable attention over the past 20 years due to their high mobility and other remarkable solid-state properties. They have potential applications in many fields, such as microelectronic devices, catalysts, organic field-effect transistors, chemical sensors, and biosensors. They have been studied as gas and volatile organic compounds (VOCs) sensors using different principles or transduction techniques, such as optical absorption, conductivity, and capacitance measurements. In this work, we report on the fabrication of gas sensors based on a conducting polymer on an interdigitated gold electrode. We use as active layer of the sensor a polythiophene derivative: poly (3-hexylthiophene) (P3HT) and analyzed its conductivity as response for exposure to dynamic flow of saturated vapors of six VOCs [n-hexane, toluene, chloroform, dichloromethane, methanol, and tetrahydrofuran (THE)]. Different responses were obtained upon exposure to all VOCs, THF gave the higher response while methanol the lower response. The influence of moisture on the measurements was also evaluated. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The sensitization of the ligand-field state of the hexaammineruthenium(II) complex ion by organic compounds

The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.

Polycyclic aromatic hydrocarbons and other selected organic compounds in ambient air of Campo Grande City, Brazil

Fourteen samples of particulate matter and semi-volatile organic compounds were collected during 6 months in the city of Campo Grande, South Mato Grosso State, Brazil. Particle-bound polycyclic aromatic hydrocarbons (PAHs) were collected on Fluoropore PTFE filters and gas-phase PAHs were collected into sorbent tubes with XAD-2 resin. Both types of samples were extracted with a dichloromethane/methanol mixture (4:1 v/v), then the extracts were subjected to gas chromatography-mass spectrometry (GC-MS) analysis. PAHs, oxidized PAH (oxy-PAHs), phenols and methoxyphenols were identified by use of GC retention indices and MS files. The average value obtained for the sum of 15 PAHs was 21.05 ng m(-3) (range: 8.94-62.5 ng m(-3)). The presence of specific tracers and calculations of characteristic ratios (e.g. [Phe]/[Phe] + [Ant]) were used to identify the sources of the emissions of PAHs in the atmospheric samples. Levoglucosan (the anhydride of beta-glucose), retene (1-methyl-7-isopropylphenanthrene) and methoxyphenols (derivatives of syringol and guaiacol) and tracers for wood burning were identified. This study demonstrates that biomass burning from the rural zone is the main source of PAHs and emissions of other substances in the investigated site of Campo Grande. (c) 2004 Elsevier Ltd. All rights reserved.

Influence of the iron source on the solar photo-Fenton degradation of different classes of organic compounds

In this work the influence of two different iron sources, Fe(NO3)(3) and complexed ferrioxalate (FeOx), on the degradation efficiency of 4-chlorophenol (4CP), malachite green, formaldehyde, dichloroacetic acid (DCA) and the commercial products of the herbicides diuron and tebuthiuron was studied. The oxidation of 4CP, DCA, diuron and tebuthiuron shows a strong dependence on the iron source. While the 4CP degradation is favored by the use of Fe(NO3)(3), the degradation of DCA and the herbicides diuron and tebuthiuron is most efficient when ferrioxalate is used. on the other hand, the degradation of malachite green and formaldehyde is not very influenced by the iron source showing only a slight improvement when ferrioxalate is used. In the case of formaldehyde, DCA, diuron and tebuthiuron, despite of the additional carbon introduced by the use of ferrioxalate, higher mineralization percentages were observed, confirming the beneficial effect of ferrioxalate on the degradation of these compounds. The degradation of tebuthiuron was studied in detail using a shallow pond type solar flow reactor of 4.5 L capacity and 4.5 cm solution depth. Solar irradiation of tebuthiuron at a flow rate of 9 L h(-1), in the presence of 10.0 mmol L-1 H2O2 and 1.0 mmol L-1 ferrioxalate resulted in complete conversion of this herbicide and 70% total organic carbon removal. (c) 2005 Elsevier Ltd. All rights reserved.