Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Analysis and Fate of Dibenzothiophene Derivatives in the Marine Environment

Abstract

Dibenzothiophene (DBT) and related methylated derivatives are known to be among the most persistent and probably the most toxic PAH in the marine environment. Their analysis and their fate by photo-oxidation and biodegradation were studied.

The methylated DBT isomers, provided that they are resolved by high resolution GC, were used as organic markers of oil pollution in oysters. The determination of the relative distribution of the four monomethyl DBT allowed to characterize the source of pollution in an oyster-area in the North Brittany (France).

The fate of methylated DBT compounds was studied in a controlled sea-water enclosure where Arabian light oil was spilled. Analysis of the weathered oil showed that: (i) oil was degraded by photo-oxidation at a rate of 0.004% day; (ii) the half-lives of photolysis of methylated DBT was dependent upon the number of methyl groups on the aromatic nucleus: 8 days for DBT, 20 days for methyl-1 DBT and more than 2 years for trimethylated DBT. Compounds solubilized in the water column were identified as methyl-substituted dibenzothiophene sulfoxides and sulfones by HPLC with synchrofluorescence and GC-flame photometric detection.

The metabolic pathway of DBT was established in vitro. Rat microsomes transformed this substrate to DBT-5-oxide and subsequently to DBT-5-dioxide. Such an enzymatic S-oxidation was shown to be principally Cytochrome-P-450 dependent. It is suggested that the mixed-function oxidase (MFO) activity of marine species could be evaluated by this S-oxidation test in addition to the usual aryl hydrocarbon hydroxylase.     

Sequential injection methodology for carbon speciation in bathing waters

A sequential injection method (SIA) for carbon speciation in inland bathing waters was developed comprising, in a single manifold, the determination of dissolved inorganic carbon (DIC), free dissolved carbon dioxide (CO₂), total carbon (TC), dissolved organic carbon and alkalinity. The determination of DIC, CO₂ and TC was based on colour change of bromothymol blue (660 nm) after CO₂ diffusion through a hydrophobic membrane placed in a gas diffusion unit (GDU). For the DIC determination, an in-line acidification prior to the GDU was performed and, for the TC determination, an in-line UV photo-oxidation of the sample prior to GDU ensured the conversion of all carbon forms into CO₂. Dissolved organic carbon (DOC) was determined by subtracting the obtained DIC value from the TC obtained value. The determination of alkalinity was based on the spectrophotometric measurement of bromocresol green colour change (611 nm) after reaction with acetic acid. The developed SIA method enabled the determination of DIC (0.24–3.5 mg C L⁻¹), CO₂ (1.0–10 mg C L⁻¹), TC (0.50–4.0 mg C L⁻¹) and alkalinity (1.2–4.7 mg C L⁻¹ and 4.7–19 mg C L⁻¹) with limits of detection of: 9.5 μg C L⁻¹, 20 μg C L⁻¹, 0.21 mg C L⁻¹, 0.32 mg C L⁻¹, respectively. The SIA system was effectively applied to inland bathing waters and the results showed good agreement with reference procedures.     

A sensitive post-column photochemical derivatization/fluorimetric detection system for HPLC determination of bisphosphonates

A new reversed-phase ion-pair high-performance liquid chromatographic (HPLC) method has been developed for the determination of the following bisphosphonic acids: alendronic acid (ALEN), etidronic acid (ETID), ibandronic acid (IBAN) and risedronic acid (RISE). Separation was achieved on a C₁₈ column using a mixture of 50 mmol L⁻¹ borate buffer pH 9.0 containing 0.25 mmol L⁻¹ tetrabutylammonium chloride and 0.5 mmol L⁻¹ EDTA and acetonitrile (97:3) as the mobile phase. The sensitive detection of the above bisphosphonic acids was based on their oxidation to orthophosphate by the on-line peroxydisulfate-assisted photolysis followed by post-column reaction with molybdate to yield phosphomolybdate. This subsequently reacted with thiamine to generate thiochrome and, finally, the fluorescence of thiochrome was measured at 440 nm with excitation at 375 nm. The developed method is precise with a mean relative standard deviation of 1.3%, sensitive (with a detection limit at the nmol L⁻¹ level), accurate, specific, rapid (analysis time approximately 13 min) and inexpensive because to the low cost of the reagents. The assay was applied to the analysis of the four bisphosphonic acids in commercial dosage formulations, in which the excipients did not interfere with the determination. The method was also applied to the determination of etidronate, risedronate and ibandronate in human urine. Sample preparation involves precipitation of the analytes from urine along with endogenous phosphates such as calcium salts by addition of calcium chloride at alkaline pH and dissolution of the precipitate in 0.05 mol L⁻¹ ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid.     

Understanding and improving direct UV detection of monosaccharides and disaccharides in free solution capillary electrophoresis

Direct UV detection of carbohydrates in free solution capillary electrophoresis at 270 nm is made possible by a photo-oxidation reaction. Glucose, rhamnose and xylose were shown to have unique UV absorption spectra hypothesizing different UV absorbing intermediates for their respective photo-oxidation. NMR spectroscopy of the photo-oxidation end products proved they consisted of carboxylates and not malondialdehyde as previously theorized and that oxygen thus plays a key role in the photo-oxidation pathway. Adding the photo-initiator Irgacure^® 2959 in the background electrolyte increased sensitivity by 40% at an optimum concentration of 1 × 10⁻⁴ mM and 1 × 10⁻⁸ mM for conventional 50 μm i.d. capillaries and for the corresponding extended light path capillaries, respectively.     

Multi-pumping flow system for the determination of dissolved orthophosphate and dissolved organic phosphorus in wastewater samples

A multi-pumping flow system (MPFS) for the spectrophotometric determination of dissolved orthophosphate and dissolved organic phosphorus in wastewater samples is proposed. The determination of orthophosphate is based on the vanadomolybdate method. In-line ultraviolet photo-oxidation is employed to mineralise organic phosphorus to orthophosphate prior to detection. A solenoid valve allows the deviation of the flow towards the UV-lamp to carry out the determination of organic phosphorus.Calibration was found to be linear up to 20 mg P L⁻¹, with a detection limit (3s_b/S) of 0.08 mg P L⁻¹, an injection throughput of 75 injections h⁻¹ and a repeatability (R.S.D.) of 0.6% for the direct determination of orthophosphate. On the other hand, calibration graphs were linear up to 40 mg P L⁻¹, with a detection limit (3s_b/S) of 0.5 mg P L⁻¹, an injection throughput of 11 injections h⁻¹ and a repeatability (R.S.D.) inferior to 2.3% for the procedures involving UV photo-oxidation.     

茂金属催化线性低密度聚乙烯的光氧化稳定性

茂金属催化线性低密度聚乙烯的光氧化稳定性;茂金属线性低密度聚乙烯;Ziegler-Natta线性低密度聚乙烯; 光氧化降解     

Enhanced Adsorption Capacity and Photo-Catalytic Oxidative Activity of Dyes in Aqueous Medium by Hydrothermally Treated Titania Pillared Clay

Titania pillared montmorillonite clay was prepared by two different routes viz. 1) conventional ion exchange method and 2) modified method wherein the post hydrothermal treatment after ion-exchange was employed. The influence of the post hydrothermal treatment on the textural properties of titania-pillared clays was studied. The calcined clay was characterized by different physico-chemical techniques such as XRD, EDX, low temperature (77 K) nitrogen adsorption and UV-Vis diffuse reflectance spectroscopy. The content of pillared titania remained unchanged irrespective of the method of preparation. The method of preparation and severity of the conditions employed for the hydrothermal treatment resulted in alteration of the crystallinity and crystallite size of the anatase. The changes in the average pore diameter was found to comensurate with the changes in crystallite size of anatase phase. The increase in total pore volume as a function of the severity of the post hydrothermal treatment resulted in the decrease in micropore volume. The severity of the post hydrothermal treatment governed the extent of the blue shift in UV-Vis DRS spectra.The behaviour of titania pillared clays in adsorptive capacity and in photo-catalytic oxidation of methylene blue and victoria pure blue in aqueous medium was studied as a function of their physico-chemical characteristics. The titania pillared clays prepared by post hydrothermal route has shown enhanced adsorption capacity and photo-catalytic oxidation.     

Synthesis of Xanthones,Thioxanthones and Acridones by a Metal-Free Photocatalytic Oxidation Using Visible Light and Molecular Oxygen

9H-Xanthenes, 9H-thioxanthenes and 9,10-dihydroacridines can be easily oxidized to the corresponding xanthones, thioxanthones and acridones, respectively, by a simple photo-oxidation procedure carried out using molecular oxygen as oxidant under the irradiation of visible blue light and in the presence of riboflavin tetraacetate as a metal-free photocatalyst. The obtained yields are high or quantitative.     

电子转移光氧化反应在有机合成中的应用

电子转移光氧化反应与光敏化的单重态氧反应是光氧化反应的两个最重要的组成部分。电子转移光氧化是随着光诱导电子转移反应研究的广泛开展而得以迅速发展的。近年来,与光诱导电子转移反应有密切关联的过渡金属配合物的可见光催化反应也已成为研究热点。一些过渡金属配合物催化的电子转移光氧化反应也已出现。本文根据电子转移光氧化反应的不同机理,对这些反应进行分类,介绍了不同类型的电子转移敏化剂(包括氰基芳烃类光敏剂、鎓盐类阳离子光敏剂、过渡金属配合物类光敏剂以及有机染料类光敏剂)引发的电子转移光氧化反应,并讨论了各类电子转移光氧化反应中底物的各种活性中间体、反应中氧的活性形式、可能的反应途径以及在有机合成中的应用。