Determination of tebufenpyrad and oxadiazon by solid-phase microextraction and gas chromatography-mass spectrometry

Summary A method for determination of trace amounts of the pesticides tebufenpyrad and oxadiazon, previous solid-phase microextraction (SPME), was developed using gas chromatographymass spectrometry and selected ion monitoring (GC-MS; SIM). Both pesticides were extracted with a fused silica fiber coated with 100 μm polydimethylsiloxane. The effects of pH ionic strength, sample volume, extraction and desorption times as well as extraction temperature were studied. The linear concentration range of application was 0.5–250 ng mL⁻¹ for both compounds, with a detection limit of 0.06 ng mL⁻¹ for tebufenpyrad and 0.02 ng mL⁻¹ for oxadiazon. SPME-GC-MS analysis yielded good reproducibility (RSD between 7.5–10.1%). It was used to check the eventual existence of tebufenpyrad and oxadiazon above this limit in water and soil samples from Granada (Spain) as well as in human urine samples. The method validation was completed with spiked matrix samples. It can be applied as a monitoring tool for water, soil and urine in the investigation of environmental and occupational exposure to tebufenpyrad and oxadiazon.     

Carrier‐Mediated Transport of Hg(II) through Bulk and Supported Liquid Membranes

The transport of Hg (II) ions from an aqueous solution into an aqueous receiving solution through bulk and supported liquid membranes containing a calix[4]arene derivative 1 as a carrier was examined. The kinetic parameters of bulk liquid membrane studies were analyzed assuming two consecutive, irreversible first‐order reactions. The influence of temperature, stirring rate, carrier concentration and solvent on the kinetic parameters (k₁, k₂, R_m ^max, t_max, J_d ^max, J_a ^max) has also been investigated. The membrane entrance rate, k₁, and the membrane exit rate, k₂, increased with increasing temperature and stirring rate. The activation energy values are calculated as 4.87 and 48.63 kj mol^?1 for extraction and reextraction, respectively. The values of calculated activation energy indicate that the process is diffusionally controlled by species. Also, the transport behavior of Hg²⁺ from aqueous solution through a flat‐sheet supported liquid membrane has been investigated by the use of calix[4]arene derivative 1 as carrier and Celgard 2500 as the solid support. A Danesi mass transfer model was used to calculate the permeability coefficients for each parameter studied. The highest values of permeability were obtained with 2‐nitrophenyloctyl‐ether (NPOE) solvent and the influence was found to be in the order of NPOE>chloroform>xylene.     

Reagentless - Continuous Determination of Aqueous Ozone with Glass Tube Separator - Thin Film Semiconductor

Abstract

A method without any reagent for the determination of ultra-trace aqueous ozone utilizing a glass tube-separation process and a thin film semiconductor is proposed. The glass tube was used as the separator to transfer ozone from water into a gas phase. Ozone was transfered into clean air flowing in the tube and then was continuously monitored at the thin film semiconductor. Signals were proportional to concentration of aqueous ozone more than 5 ppb. Detection limit (S/N=3) was 0.02 ppt for aqueous ozone. The relative standard deviation (n=7) was 3.8 % at 7.6 ppb. The interference from hydrogen peroxide. monochloramine. and dichloramine were completely eliminated. The sensitivity of aqueous ozone was 45 times greater than that of hypochlorite.     

Continuous Flow Determination of Residual Aqueous Ozone With Membrane Separation-Chemiluminescent Detection

Abstract

A method for the determination of ultra-trace aqueous ozone utilizing a membrane-separation process and a chemiluminescent detector is proposed. The microporous PTFE tube was used as separator to transfer aqueous ozone into a gas phase. Air bubbling was used to enhance the separation. Chemilumi nescent signals produced from the reaction of ozone with ethylene in air were linearly proportional to concentration of aqueous ozone from 8 ppb to 9.5 ppm. The relative standard deviation (n=4) was 3.5% at 0.2 ppm. The time it took from starting the sample flow until the signal to reach a stable level was 1.5 min. The interference from chromium(VI), manganese(VII), chlorine, bromine, phthalate, and sulfophthalate was completely eliminated.     

Electrochemical and Spectroscopic Studies of Co(CREATININE)2Cl2

The electrochemical behavior of Co(creatinine)₂Cl₂ was investigated by cyclic voltammetry in organic solvents (DMSO and DMF) and in aqueous solution. Analysis of the results indicates that the electroactive species depend on the nature of the solvent. In DMF a single reduction process Co(II)/Co(I) is observed. In DMSO the redox behavior of the complex changes with the scan rate and a two-electron transfer process can be eventually observed. In aqueous solution the complex immediately decomposes giving rise to the aquo-cation. The characteristic peak of the redox couple Cl₂/Cl^? is observed as a consequence of the chloride released from the coordination sphere. Analysis of the electronic spectra gave additional support to the proposed mechanisms. The Co-Cl and Co-N stretching bands were clearly identified in the low frequency region of the IR spectrum.     

NMR Relaxation Studies in Aqueous Solutions of Amino Acids

Abstract

The proton magnetic resonance (PMR) spin-lattice and spin-spin relaxation times (T1 and T2) were measured in aqueous solutions of glycine and L-proline as a function of solute concentrations and at a temperature of 32°C. The relaxation times were measured using Bruker PC 120 NMR process analyser. The relaxation times were found to decrease with increase of solute concentrations. The results are interpreted on the basis of flickering cluster model and hydrogen bond formation between solute and solvent molecules.     

A four-coordinate cadmium(II) polymer for efficient adsorption of Congo red,kinetic, isotherm,fluorescence and antibacterial activity

A 3-D cadmium-based coordination polymer, [CdCl₂L]_n (1) (where L = 1,1-(1,6-hexanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole-2-thione), was synthesized and structurally characterized. The capability of the polymer as an efficient sorbent for Congo red (CR) removal from aqueous solution has been evaluated. Compound 1 has a tetrahedral arrangement with a CdS₂Cl₂ core. L in 1 is bidentate to two neighboring Cd^II centers via the methimidazole sulfurs to create 1D chains propagating along the c-axis. The remaining coordination sites are occupied by two terminal chlorides. The chains are further stabilized by intermolecular C–H?Cl hydrogen bonds between the chlorides and hydrogens of the imidazole rings. Parallel chains stack in the 3-D structure. The Cd^II polymer sorbent was characterized by infrared spectroscopy, elemental analysis, UV–vis, solid fluorescence and X-ray single-crystal diffraction. Sorption kinetics were studied by three kinetic models, second order, Elovich and intraparticle diffusion. The results indicate that the mechanism of the sorption process followed Elovich kinetic model. Sorption equilibrium was also studied with Langmuir, Temkin, and Freundlich isotherm models. The sorption process followed the Temkin isotherm. MIC, MBC, and DNA cleavage activities of 1 were also studied. Furthermore, the UV–vis and solid state fluorescence spectra of 1 were measured.     

Photocatalyzed reaction of indole in an aqueous suspension of titanium dioxide

The photocatalyzed oxidation of indole (1) in an aqueous suspension of titanium dioxide has been investigated and an attempt has been made to identify the products formed during the photooxidation process by gas chromatographic–mass spectrometric (GC–MS) analysis. Photolysis of an aqueous solution of indole (1) in the presence of titanium dioxide and oxygen led to the formation of 2,3-dihydroindole-2-one (6) and 1H-indole-2,3-dione (7). A probable pathway for the formation of these products has been proposed.     

Suzuki–Miyaura Reaction of Unactivated Aryl Chlorides Using Benzimidazol‐2‐Ylidene Ligands

Abstract

Four functionalized bis(benzimidazolium) salts (2a–d) have been prepared and characterized by conventional spectroscopic methods and elemental analyses. A highly effective, easy to handle, and environmentally bengin process for palladium‐mediated Suzuki cross‐coupling was developed. The in situ prepared three‐component system Pd(OAc)₂/bis(benzimidazolium) bromides (2a–d) and Cs₂CO₃ catalyzes quantitatively the Suzuki cross‐coupling of deactivated aryl chloride in aqueous media.     

Concise Synthesis of α-(Hydroxymethyl) Alkyl and Aryl Vinyl Ketones

2,4-Diketoesters 2 have first been reported as starting materials for the synthesis of a new class of α-hydroxymethyl-α,β-unsaturated ketones 3. Thus, under heterogeneous liquid–liquid medium in the presence of concentrated aqueous potassium carbonate as a base, both aliphatic and aromatic 2,4-dioxoalkanoates 2 react with aqueous formaldehyde to afford the corresponding ketones 3 in fair to good yields.     

Improved preparation of 2 M triethylammonium bicarbonate

ABSTRACT

The widely used chromatographic eluent, aqueous triethylammonium bicarbonate, can be efficiently prepared as 2?M stock solution by carbonation of a mixture of triethylamine and water in a commercially available pressure reactor (20–25?psi). This improved process reduces carbon dioxide waste emissions by ca. 90% compared to traditional gas bubbling at atmospheric pressure.     

Determination of Polychlorinated Biphenyls in Paper Mill Effluents and Process Streams

Abstract

Special techniques have been found necessary for isolating PCB's from cellulose fiber-containing effluents and process streams and for determining PCB's in effluents from paper mills using recycled fiber. Sources of potential PCB loss from aqueous solutions are revealed and means of avoiding these losses are proposed.

Significant amounts of PCB remained on cellulose fibers following separatory funnel extraction of a fiber-water suspension with hexane or methylene chloride-hexane. Reflux of the fibers with alcoholic KOH was necessary to remove the remaining PCBs. PCB losses due to volatilization from aqueous solution occurred during analysis, but these were minimized by working in a cool environment and covering the Sample with a layer of hexane. The presence of cellulose fibers in PCB-containing effluents enhanced the effluents' stability during storage.

Chromium trioxide oxidation was found to be valuable in cleaning up extracts from paper mill effluents. Perchlorination is apt to yield misleading results.     

Molecular Recognition Studies on Supramolecular Systems. 29. Anilino- and m-Toluidino-β-Cyclodextrins: Structural and Conformational Analyses and Molecular Recognition of Aliphatic Alcohols

Abstract

Mono(6-anilino-6-deoxy)-β-cyclodextrin (1) and mono[6-(m-toluidino)-6-deoxy]-β-cyclodextrin (2) were synthesized and characterized. Circular dichroism and fluorescence spectral studies and fluorescence lifetime measurements have been performed to elucidate the conformations of 1 and 2 in aqueous buffer solution. 1-D and 2-D NMR spectra of 2 have been measured in D₂O to deduce its structure and detailed conformation in solution. From the circular dichroism, fluorescence, and NMR spectroscopic studies, it was revealed that the substituents appended to 1 and 2 penetrate into the cyclodextrin cavity forming a stable self-inclusion complex in aqueous solution, and also that the short linkage between the m-toluidino and cyclodextrin moieties makes the cyclodextrin ring of 2 deformed to some extent. The complex stability constants (K _S) of 1 and 2 for a series of aliphatic alcohols have been determined by using spectropolarimetric titrations in aqueous phosphate buffer solution (pH 7.20) at 25°C to elucidate the role of introduced substituents and the weak interactions involved in inclusion complexation by the modified cyclodextrins. The results obtained indicate that the van der Waals and hydrophobic interactions mainly contribute to the formation of complexes between the cyclodextrins and aliphatic alcohols, and the inclusion complexation process involves the induced-fit mechanism. Modified β-cyclodextrin 2 can recognize not only the size, shape, and hydrophobicity of the guest molecules, but also chiral guests, affording a moderate enantioselectivity of 1.55 for (+)/(-)-borneol.     

Ultraviolet Photo-Induced Fluorescence Followed by Laser Excitation (UV-PIF-LE) for the Determination of Pesticides in Natural Waters

Abstract

A new method was developed for determining trace amounts of pesticides, using an ultraviolet (UV) lamp to obtain photo-induced fluorescent (PIF) compounds, and then using laser excitation (LE) by a tunable source to excite and simultaneously characterize their fluorescence over a short acquisition time using an intensified charge-coupled device camera. This new UV-PIF-LE method was applied to determine isoproturon, oxadiazon, and fipronil in natural waters. This approach represents an improvement on the previously published direct laser photo-induced fluorescent (DL-PIF) approach that utilized the inclusion of a supplementary UV irradiation device in the experimental setup, permitting the separation of the formation and detection steps for the PIF analytes. This evolution improves the selectivity and increases the sensitivity while maintaining a short analysis time. The UV-PIF-LE method gave very good results with satisfactory analytical performance for the determination of the selected pesticides. This approach also demonstrated good reproducibility, with relative square deviation values between 3.3% and 6.3%, for spiked river water and seawater samples with detection limits in the ng mL^?1 range.     

Isocratic HPLC Separation of Scopoletin and Cis/Trans Isomers of Ferulic Acid as Well as Isoscopoletin and Cis/Trans Isomers of Isoferulic Acid

Abstract

Cis/trans isomers of ferulic and isoferulic acids and their corresponding coumarins, scopoletin and isoscopoletin, were separated by isocratic High Performance Liquid Chromatography using RP-8 (5 μm) as a stationary phase and aqueous methanol or aqueous acetonitrile as a mobile phase. The UV spectrum of cis-isoferulic acid was obtained by a photodiode array detector.     

Selective Determination of Organic and Inorganic Thiocyanates in Aqueous Solution by IR Spectrophotometry

Abstract

A new spectrophotometric method for the determination in aqueous solution of both organic and inorganic thiocyanates is described. Organic thiocyanates are determined by measuring at wavenumber of 2150 cm^?1 the absorption of solutions directly extracted with carbon tetrachloride. Inorganic thiocyanates require a previous derivatization reaction with dimethylsulfate, and are determined as methylthiocyanates. The method is quick, accurate and selective. The results obtained suggest its utilization in analysis of aqueous samples.     

蝴蝶形单分子配合物的合成、晶体结构及其对水溶液中有害离子的检测

用苯并咪唑基配体5,5′-二(2-苯并咪唑基)-2,2′-联吡啶(H2L)与镍、锌离子溶剂热合成了配合物[Ni(HL)(HCOO)(H2O)](1)和[Zn(H2L)(H2O)2](NO3)2(2)。X射线单晶测试表明镍与锌配合物的晶体结构是只含一个配体和一个金属离子的蝴蝶形单分子。配合物分子之间存在大量分子间氢键,配合物1通过分子间氢键连接成了二维层状结构,配合物2通过分子间氢键连接成了三维超分子结构。配合物1和2在水溶液中很稳定,且能够微溶于水。荧光测试表明配合物2的固体及在水溶液中都具有很强的荧光性质,且能够在水溶液中高选择性、高灵敏度检测有害重金属离子Hg^2+及氧化性阴离子Cr2O7^2-。     

Solubilization and reaction studies of polar substrates in the presence of apolar octahydroxy reverse micelles

Octahydroxy tetrameric cyclophane1 containing four cetyl chains was synthesized from resorcinol and cetanal under acidic conditions and was characterized by¹HNMR,¹³CNMR, and elemental analysis. Cyclophane1 forms aggregates with CMC 7.1 × 10^–5 M in a nonpolar solvent such as CCl₄. The smaller molecule glycine is more solubilized than the bigger lysine, demonstrating size discrimination. The highly polar compounds aspartic acid and glutamic acid, however, required 1.5 mm of1 for solubilization at the detectable limit. Kinetic study of the oxidation of glycine by ninhydrin in the presence of1 revealed that the rate enhancement compares to that in an aqueous environment, whereas the reduction of crystal violet by Hanzchester shows a decrease in the rate over that in aqueous solution.     

Supramolecular isomerism in the hydrogen-bonded network of (5<Emphasis Type="Italic">R</Emphasis>,10<Emphasis Type="Italic">R</Emphasis>)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-<Emphasis Type="Italic">cde</Emphasis>]chromene monohydrate

A new compound (5R, 10R)-3,8-dihydroxy-5,10-diethoxy-5,10-dihydrochromeno[5,4,3-cde]chromene monohydrate was obtained from 3,4-dihydroxybenzaldehyde in aerobic basic aqueous ethanol solution in the presence of manganese chloride and triethylamine and crystallized in orthorhombic P2₁2₁2₁ space group (denoted as 1). When 1 was recrystallized from aqueous methanol, it was transformed to another crystal (2) with the same composition but in P2₁/n space group. The drastic difference in the extensive hydrogen bond network makes 1 a 3D and 2 a 2D infinite supramolecular structure, respectively.     

Self-assembly of zinc chlorophyll derivatives possessing a pyrenyl group at the 17-propionate residue and effects of additional γ-cyclodextrins on their optical properties

Two kinds of zinc 3¹-hydroxy-13¹-oxo-chlorins 1 and 2 possessing a pyrenyl group at the 17-propionate residue, of which the linker length between the chlorin and the pyrene moieties was varied, were synthesised from naturally occurring chlorophyll a, and were self-assembled in an aqueous solution. Both zinc chlorins 1 and 2 exhibited Q_y absorption bands around 720 nm accompanying circular dichroism signals in the Q_y region, indicating that these zinc chlorins could form self-aggregates like chlorosomes of green photosynthetic bacteria. Addition of γ-cyclodextrin into an aqueous solution containing the self-aggregates of zinc chlorin 1 esterified with 1-pyrenylmethanol induced the appearance of excimer emission of the pyrene moieties around 480 nm as well as increased the fluorescence intensities of the pyrene monomers at 378 and 396 nm, while only an increase in fluorescence from the monomeric pyrene moiety was observed in the case of 2 esterified with 4-(1-pyrenyl)butanol. Exogenous γ-cyclodextrin unchanged the spectral features derived from the chlorin moieties of 1 and 2 in the aqueous phase. These suggest that the encapsulation of the pyrenyl groups in the zinc chlorins unchanged their assembling states under the present conditions.