Prediction of molecular structures of aza-arenes by retention indices and fluorescence spectra

Two methods are described for predicting the molecular structures of aza-arenes eluted from a capillary column. The first is based on a combination of retention indexes (RI) and a post-column reaction. The RI of an aza-arene is calculated by using the incremental contributions of some atomic groups to RI. Once the molecular weight is determined by the mass spectrum, the possible compounds are picked up, based on comparison of the observed RI with the calculated RI values and information about the intramolecular environment around the nitrogen atom obtained from the degree of peak shift resulting from interaction with Ni(II). The second is due to combination of information from fluorescence spectrometry and TLC fractionation. The fluorescence spectrum allows the identification of the fused ring system.     

系列羟基苯基卟啉的合成及其荧光光谱研究

按等物质的量比混合两种醛, 采用一步法设计并合成出系列中位取代的对-羟基苯基卟啉, 产物经薄层层析分析表明: 包括六种卟啉配体混合物, 以中性氧化铝为固定相, 采用不同体积比的氯仿和乙醇为淋洗剂, 对六种卟啉配体混合物进行分离, 用波谱方法对六种化合物的结构加以确认. 研究了六种卟啉配体的荧光光谱, 结果显示在440 nm的荧光强度很弱, 随着卟啉周边羟基的增加而增加; 在650 nm的荧光强度很强, 随着卟啉周边羟基的增加而减弱.     

A Study On Air Pollution by Asphalt Fumes

Abstract

A TLC/HPLC procedure for the determination of polycyclic aromatic hydrocarbons (PAH), occuring in asphalt fumes (adsorbed on particular matter), is described. The method is based on extraction of asphalt fume particles, collected on glass fibre filters, using CCK₄. Following a clean up step by the aid of a TLC procedure on Al₂ O₃ thinlayer plates, using a mixture of cyclohexane/acetone/ether as the mobile phase. Under UV-light, occuring PAH are indicated as fluorescent spots. A separation of the collected PAH into individual components and their identification is performed by the aid of a HPLC procedure. Futher-more, an approach was made to verify the separated PAH by their fluorescence spectra and their mass spectra.     

Determination of aflatoxins in food products by chromatography.

Several chromatographic methods for the determination of aflatoxins in agricultural and food products are reviewed. During the past two decades, identification and determination of aflatoxins were done by thin-layer chromatography (TLC) because it was easy, fast and inexpensive. However, high-performance liquid chromatography (HPLC) using fluorescence detection is now the method of choice for determining aflatoxins and is also growing in popularity for their identification. The reasons for selecting HPLC over TLC can be summarized as the ability to analyze for a wide variety of compounds, including compounds that are easily degraded by heat, light or air, the ease of adaptation to confirmatory procedures, the potential for automation and the dramatic improvement in instrumentation, including the development of increasingly sensitive fluorescence and electrochemical detectors and short, high-resolution, reversed-phase columns.     

Analysis of atmospheric pollutants with coupled gas chromatography-atomic absorption or thermodesorption-gas chromatography

We have perfected a specific and original analytical method suitable for organic and inorganic compounds using sampled run-off water collected nearby a filling station. The dissolved lead species are volatilized by substituting the inorganic ligands with hydrogen, using sodium-borohydride in a suitable reaction medium (H2O2, KOH). The volatile lead hydrides are then trapped on a gas chromatographic column filled with Chromosorb W impregnated with 2% of OV 275 and immersed in liquid nitrogen. After desorption, the products are analysed by atomic absorption spectroscopy. We have carried out the analysis of aldehydes mixtures, sampled from a smog chamber. They are trapped, at room temperature, in a glass column filled with Tenax. These pollutants are then heated at 250 degrees C under a flow of nitrogen, and trapped again in a melted silica capillary column at -110 degrees C. This trapping being over, the column is drastically heated at 200 degrees C, which drives the products into the capillary column of a gas-chromatograph apparatus. This method has also enabled us to carry out a direct analysis of these pollutants sorbed on particles which have been placed into the glass column. this thermodesorption-gas chromatography system, coupled with a mass-spectrometry apparatus, allows us to identify and analyse most atmospheric pollutants.     

Polycyclic Aromatic Hydrocarbons Formation from Fuel and Additives Combustion

A study has been made of the effect of additives to the fuel of a turbulent diffusion flame on the formation of soot and polycyclic aromatic hydrocarbons (PAHs). Fuels containing a polystyrene thickener doped with benzene proved to have many advantages over unthickened fuels. Most significant were an increase in the burning time and the flash point. Nevertheless, polystyrene and benzene additives to a considerable extent increased the formation of soot and PAHs. The analysis of PAHs in this study was made by capillary gas chromatography (GC) and capillary gas chromatography/mass spectrometry (GC/MS). A total of 42 individual compounds were characterized by their retention indices and mass spectra.     

Structure-type separation of diesel fuels by solid phase extraction and identification of the two- and three-ring aromatics by capillary GC-mass spectrometry

A simple and effective solid phase extraction (SPE) method using silica gel micro glass columns has been developed for the separation of diesel fuel into groups of aliphatic, and mono-, di- and polyaromatic hydrocarbons. It is based on a stepwise gradient of dichloromethane in n-pentane. The resulting fractions were analyzed by capillary gas chromatography with a flame ionization detector and coupled gas chromatography-mass spectrometry. Commercially available standards, and retention indices and mass spectra were used for identification of individual aromatic compounds. The principal polycyclic aromatic hydrocarbons (PAHs) in diesel fuel are naphthalene, biphenyl, fluorene, phen-anthrene and their alkylated derivatives. Sulfur-containing PAHs are mainly represented by methyl-substituted dibenzo-thiophenes.     

Analysis of siloxane pyrolysis products by cryo-GC/FT-IR and GC/MS

On line measurements of infrared and mass spectra of siloxane pyrolysis products separated by gas chromatography are described. The FT-IR absorbance spectra have been recorded from the eluates trapped as small spots on a moving window held at 77 K. Three of the main compounds separated were selected for FT-IR identification performed by comparing the spectra with GC/MS data and by spectral searching using a library of compounds measured under the same conditions.Dedicated to our most honourable teacher Professor Dr. H. Kriegsmann on the occasion of his 70th birthday     

Laser-induced site-selection matrix-isolation fluorescence spectrometry of dibenzacridine isomers

Laser-induced matrix-isolation site-selection fluorescence spectrometry is used to obtain narrowed-line spectra, linear dynamic ranges and limits of detection for four isomeric dibenzacridines in argon at 15 K. Site-selection fluorescence is used to determine dibenzacridines in two synthetic mixtures, a four-component mixture of the isomeric dibenzacridines and a thirteen-component polycyclic aromatic hydrocarbon mixture. The capabilities of site-selection and Shpol'skii fluorescence spectrometry for the identification and determination of aza-arenes in complex mixtures are compared.     

Neue cannabinoide—1

Extracts of cannabis contain—as was shown by glass capillary chromatography—a number of so far unknown cannabinoids. They were obtained in pure state by micropreparative gas chromatography followed by thin layer chromatography. The new compounds were characterized by their mass spectra. The structures of four of these compounds were determined by mass spectra, NMR-spectra and microchemical reactions followed by an investigation of the reaction products by gas chromatography-mass spectrometry. The new compounds are:Cannabichromanon = 2,2-Dimethyl-5-hydroxy-3-(3-oxo-butyl)-7-pentyl-4-chromanon (1)Cannabifuran = 1-Hydroxy-9-isopropyl-6-methyl-3-pentyl-dibenzofuran (3)Dehydrocannabifuran = 1-Hydroxy-9-isopropenyl-6-methyl-3-pentyl-dibenzofuran (4)2-Oxo-Δ³-THC = 2-Oxo-Δ³-tetrahydrocannabinol (5)     

Two-dimensional LC-MS/MS in detection of peptides in hypothalamus of the rat subjected to hypoxic stress

A capillary 2-D LC method coupled with IT MS has been used for separation and identification of peptides in rat hypothalamus. Animals of two different age groups (8 and 50 wk) were exposed to two different rates of CO(2 )in inhaled air to investigate the influence of different hypoxia/hypercapnia levels and their stress-related factor on the peptide excretion. Peptide compounds were fractionated (strong cation exchange chromatography), trapped, and separated (RP chromatography), and MS/MS mass spectra were used for identification. About 107 peptide compounds were identified and 88 of them were semiquantified. Among the characterized peptides, there were fragments from proteins such as proenkephalin A, proSAAS, prosomatostatin, prooxytocin, vasopressin, etc. Explorative principal component analysis (PCA) combined with hypothesis testing was applied to the obtained data to investigate the impact of age and hypoxic stress factors on the peptide pattern. Twenty-six peptides revealed significant differences in concentrations between the animal groups influenced by age and influx rate.     

Identification of neuropeptides in rat brain rhinencephalon

A capillary two-dimensional liquid chromatography method coupled with ion trap mass spectrometry has been used for separation and identification of neuropeptides in rat rhinencephalon. Animals of three different age groups were exposed to slow and quick CO2 influx. The neuropeptides were extracted by solid phase extraction and the purified extracts were analysed by 2-D HPLC. The compounds were fractionated (strong cation exchange column), trapped and separated, and MS/MS fragment mass spectra were used for identification. About thirty peptide compounds were identified. A significant difference between concentration levels of "stressed" (quick CO2 influx) and "non-stressed" (slow CO2 influx) rats was found for 25 of the identified peptides.     

Quantitation of polyamines using thin-layer chromatography and image analysis

Efficient separation of dansylated polyamines can be achieved by thin-layer chromatography (TLC). Quantitation, however, can be laborious because it requires removal of the silica gel and the fluorescing derivative from the glass plates, elution in a suitable solvent, and estimation with a fluorescence spectrophotometer. We report here a relatively simple and rapid method for the quantitation of dansylated polyamines that employs an image analyzer without removal from the glass TLC plates.     

A sampling system using sample vials for high-temperature isothermal capillary gas chromatography

A novel sampling system for isothermal capillary gas chromatography of medium- or low-volatility mixtures is described and test results are reported using flame ionization detection. The system features a loading and positioning chamber for glass vials which can carry a dilute sample in up to 0.2 ml of a volatile solvent. The output from the glass vaporization chamber is trapped onto a packed precolumn operated in the backflush mode. The analytes are further transferred over a wall-coated capillary trap prior to isothermal capillary GLC. Repeat-cycle operation of the sampling system requires 10 channels of a processor for time control over 5 solenoid valves and 3 static heaters. Preliminary results with long-chain n-alkanes in the submicrogram range showed no unwanted effects. The principal claim of the system is an improved rejection of non-volatiles.     

Rapid,simple, and highly sensitive analysis of drugs in biological samples using thin-layer chromatography coupled with matrix-assisted laser desorption/ionization mass spectrometry

Rapid and precise identification of toxic substances is necessary for urgent diagnosis and treatment of poisoning cases and for establishing the cause of death in postmortem examinations. However, identification of compounds in biological samples using gas chromatography and liquid chromatography coupled with mass spectrometry entails time-consuming and labor-intensive sample preparations. In this study, we examined a simple preparation and highly sensitive analysis of drugs in biological samples such as urine, plasma, and organs using thin-layer chromatography coupled with matrix-assisted laser desorption/ionization mass spectrometry (TLC/MALDI/MS). When the urine containing 3,4-methylenedioxymethamphetamine (MDMA) without sample dilution was spotted on a thin-layer chromatography (TLC) plate and was analyzed by TLC/MALDI/MS, the detection limit of the MDMA spot was 0.05 ng/spot. The value was the same as that in aqueous solution spotted on a stainless steel plate. All the 11 psychotropic compounds tested (MDMA, 4-hydroxy-3-methoxymethamphetamine, 3,4-methylenedioxyamphetamine, methamphetamine, p-hydroxymethamphetamine, amphetamine, ketamine, caffeine, chlorpromazine, triazolam, and morphine) on a TLC plate were detected at levels of 0.05 − 5 ng, and the type (layer thickness and fluorescence) of TLC plate did not affect detection sensitivity. In addition, when rat liver homogenate obtained after MDMA administration (10 mg/kg) was spotted on a TLC plate, MDMA and its main metabolites were identified using TLC/MALDI/MS, and the spots on a TLC plate were visualized by MALDI/imaging MS. The total analytical time from spotting of intact biological samples to the output of analytical results was within 30 min. TLC/MALDI/MS enabled rapid, simple, and highly sensitive analysis of drugs from intact biological samples and crude extracts. Accordingly, this method could be applied to rapid drug screening and precise identification of toxic substances in poisoning cases and postmortem examinations.     

The palladium/silver membrane focusing injector — A new inlet system for thermal desorption capillary gas chromatography

Summary A new sample focusing technique for capillary gas chromatography is described. The system is designed as a focusing inlet for thermally desorbed gas samples. A solid-sorbent trapped sample is thermally released from the sample tube, transferred to a palladium/silver membrane chamber by a hydrogen carrier gas stream and retained there by the gas separation membrane, which is highly permeable to the carrier gas. After focusing in the membrane chamber the sample is injected onto the separation column. This technique allows focusing and injection of highly volatile compounds in capillary gas chromatography without using any coolant. The injection performance for n-alkanes is shown to be comparable to the cryofocusing technique.     

Fluorescence observation supporting capillary chromatography based on tube radial distribution of carrier solvents under laminar flow conditions

We developed a capillary chromatography system by using an open capillary tube made of fused-silica, polyethylene, or polytetrafluoroethylene, and a water-hydrophilic/hydrophobic organic mixture carrier solution, called tube radial distribution chromatography (TRDC) system. By comparing with chromatograms obtained via the TRDC system, fluorescence photographs and profiles of the fluorescent dyes dissolved in the carrier solvents in capillary tubes were observed under laminar flow conditions. The chromatograms were obtained for a model mixture analyte consisting of 1-naphthol and 2,6-naphthalenedisulfonic acid with the TRDC system, by using a fused-silica capillary tube and a water-acetonitrile-ethyl acetate carrier solution. By altering the carrier flow rates, we examined the fluorescence photographs and profiles of the dyes, perylene and Eosin Y, dissolved in the carrier solvents in the capillary tube by using a fluorescence microscope equipped with a CCD camera. As confirmed by fluorescence observations, the major inner and minor outer phases generated in the capillary tube were based on the tube's radial distribution of the carrier solvents. We designed and manufactured a microreactor incorporating microchannels in which three narrow channels combined to form one wide channel. When the carrier solvents containing the dyes were fed into the channels, the inner and outer phase generations were also observed in the narrow and wide channels, strongly supporting the conclusions concerning the tube radial distribution phenomenon of the solvents.     

XAS study on copper red in ancient glass beads from Thailand

Glass has been used in ornaments and decorations in Thailand for thousands of years, being discovered in several archeological sites and preserved in museums throughout the country. To date only a few of them have been examined by conventional methods for their compositions and colorations. In this work we report for the first time an advanced structural analysis of Thai ancient glass beads using synchrotron X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray (EDX) spectrometry. Four samples of ancient glass beads were selected from four different archeological sites in three southern provinces (Ranong, Krabi and Pang-nga) of Thailand. Archaeological dating indicated that they were made more than 1,300 years ago. A historically known method for obtaining a red color is to add compounds containing transition elements such as gold, copper, and chromium. For our samples, EDX spectrometry data revealed existing fractions of iron, copper, zinc, and chromium in ascending order. Thus, copper was selectively studied by XAS as being potentially responsible for the red color in the glass beads. K-shell X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of copper were recorded in fluorescence mode using an advanced 13-element germanium detector. Comparisons with XANES spectra of reference compounds identified two major forms of copper, monovalent copper and a metallic cluster, dispersed in the glass matrix. The cluster dimension was approximated on the basis of structural modeling and a theoretical XANES calculation. As a complement, EXAFS spectra were analyzed to determine the first-shell coordination around copper. XAS was proven to be an outstanding, advanced technique that can be applied to study nondestructively archaeological objects to understand their characteristics and how they were produced in ancient times.