Analysis of Organic Matter in Water of Low TO C (Total Organic Carbon) Content by Chromatographic Techniques

Abstract

The problems encountered when analyzing organic pollutants in drinking water stem from the large number of unknown compounds at very low concentration.

The concentration of the organics is carried out on n-alkyl silica, after a rigorous cleaning, or by liquid-liquid extraction. The complexity of these extracts renders a direct analysis by gas chromatography coupled with mass spectrometry impossible; hence, a pre-separation step is required.

Reversed and normal phase chromatography have been investigated with these extracts. The former leads to informative fingerprints but subsequent identification is difficult.

Normal phase liquid chromatography is more suitable and a separation by chemical classes of increasing polarity is applied to water extracts. The eluent is fractionated, each fraction is then gently evaporated and subsequently analyzed by GC. Identification is then possible by coupling with mass spectrometry.

These procedures are used to follow the change in organic matter during the two last steps of the drinking water treatment: ozonation and filtration on active charcoal. Another application is the analysis of humic extracts.     

Capillary Column Gas Chromatography of Environmental Polycyclic Aromatic Compounds

Abstract

The methodologies are described for isolating clean fractions of polycyclic aromatic compounds from diverse environmental samples such as air particulate matter, sediments, and fish tissue. The common step in all procedures is the separation of the polycyclic aromatic compound fraction into well-defined chemical classes by adsorption chromatography on an alumina column. These procedures greatly facilitate the detailed characterization of the polycyclic aromatic hydrocarbons, sulfur heterocycles, and nitrogen heterocycles by capillary column gas chromatography.     

Determination of Pesticides in Carrots by Gas Chromatography–Mass Spectrometry

ABSTRACT

A sensitive and selective method was developed to determine pesticides in carrots by gas chromatography–mass spectrometry following the development of an optimized extraction procedure. The method was validated for 30 organochlorine pesticides for gas chromatography with electron capture detection obtaining limit of detection from 0.18 to 0.92?µg/kg except for cis- and trans-permenthrin. Twenty-six carrot samples were analyzed and six pesticides were detected. The results compared with the accepted maximum residue levels in correlation to crop origin.     

High temperature treatment allows the detection of episesamin in paulownia wood extractives

Abstract

The composition and the relative variation of secondary metabolites of Paulownia tomentosa S. wood under thermal effect is a little explored area. Wood material was previously thermo-treated at 210?°C for 3?hours using a press vacuum technology. Extractives of untreated and thermo-treated wood material achieved with Soxhlet extraction techniques were obtained. Then the extracts were chromatographed by using thin layer chromatography. Component groups in extracts were determined by gas chromatography in combination with mass spectrometry. In terms of wood change the thermo-treatment of wood induces a darkening of wood color surface (ΔL* = 28.3), an increase of mass loss (3.5%) and an increase of the amount of extractives and lignin content as well as an increase of the chloroform soluble fraction. This work mainly describes the chemical exploration of the extract from paulownia wood, leading to the isolation and identification of episesamin.     

Cytotoxic agents for KB and SiHa cells from n-hexane fraction of Cissampelos pareira and its chemical composition

Eleven constituents were characterised by gas chromatography–mass spectrometry analysis, and five molecules were isolated using column chromatography. The in vitro study of the extract and isolated molecules against KB and SiHa cell lines revealed oleanolic acid (1) and oleic acid (2) as potent cytotoxic molecules with potential anticancer activity. The IC₅₀ values of n-hexane extract (CPHF), oleanolic acid (1) and oleic acid (2) were >300, 56.08 and 70.7 μg/mL (μM), respectively, against KB cell lines and >300, 47.24 and 80.2 μg/mL (μM), respectively, against SiHa cell lines.     

Bioassay-guided isolation of antibacterial constituents from Diospyros lotus roots

The aim of this study was to explore the extract/fractions and compounds of Diospyros lotus against various Gram-positive and Gram-negative bacteria strain. The results showed marked susceptibility of extract and its fractions against test pathogens. Among them, chloroform fraction was most dominant and effective against all tested bacteria. The chloroform fraction was subjected to column chromatography which led to the isolation of lupeol (1), 7-methyljuglone (2), β-sitosterol (3), stigmasterol (4), betulinic acid (5), diospyrin (6) and 8-hydroxyisodiospyrin (7). Among the isolated compounds, betulinic acid (5) showed significant activity against most of the tested pathogen. In conclusion, our study validated the traditional uses of the plant in the treatment of infectious diseases which was also strongly supported by the isolated compound, betulinic acid (5).     

Vertical Distributions of Nonmethane Hydrocarbons Over Western Europe: Seasonal Cycles of Mixing Ratios and Source Strengths

Abstract

Airborne measurements of the vertical and horizontal distributions of nonmethane hydrocarbons and methyl chloride over western Europe are reported. Annual emission cycles have been calculated from the seasonal variations of mixing ratios using a simple one-dimensional two-box model. They indicate natural sources of ethene, propene, i-butane, i-pentane, and methyl chloride. Grab samples were analysed by subambient temperature programmed gas chromatography.     

Separation of polar antioxidants from Rhizoma Polygonatum Odorati by high-speed counter-current chromatography with a hydrophilic solvent system

Some highly polar compounds are quality control makers for medicinal herbs. However, investigation of them has been hampered because the existing fractionation steps are difficult and laborious to purify them. Similar situations happen to Rhizoma Polygonatum Odorati, a widely used food supplement and medicinal herb with strong antioxidant activity, and up to date, only ethyl acetate fraction of Rhizoma Polygonatum Odorati has been comprehensively investigated. Here, HSCCC using a hydrophilic solvent system composed of n-butanol–ethanol–2 M ammonium sulfate (1:1:2, v/v/v) was performed to isolate highly polar antioxidants in n–butanol fraction of Rhizoma Polygonatum Odorati, guided by DPPH–HPLC experiment. Afterward, Sephadex LH-20 column chromatography eluted by methanol was selected to eliminate ammonium sulfate and purify co-eluted compounds in HSCCC collected fractions. Finally, nine compounds, including four nucleosides, cytidine (1), uridine (4), guanosine (5), and adenosine (8); two nucleobases, guanine (3), and adenine (6); and three amino acids, tyrosine (2), phenylalanine (7), and tryptophan (9) with purities over 98% were achieved and identified by UV, MS, and ¹H NMR data. Notably, compounds 1–9 were first reported in genus Polygonatum. The results indicated that the proposed method was an efficient approach to isolate and purify highly polar compounds from complex extracts.     

Isolation and Characterization of Sulfur-Containing Polycyclic Aromatic Compounds (Thia-Arenes) from Complex Environmental Mixtures

Abstract

A multi-dimensional chromatographic method was developed and applied to the separation of thia-arenes and polycyclic aromatic hydrocarbons (PAH) derived from coal tar. A thia-arene-rich fraction, prepared using a combination of alumina chromatography and palladium chloride/silica gel chromatography, was further separated using normal phase HPLC to isolate fractions containing thia-arenes with molecular masses ranging from 184 amu to 284 amu. These fractions were analysed using gas chromatography-mass spectrometry; approximately one-half of the thia-arenes in a coal tar extract were retained and separated by the palladium chloride-silica gel step. This methodology has been successfully applied to coal tar, air particulate material, sediments and biological samples.     

Two Stabilized Calix[6]Cryptand Stereo Isomers used as Stationary Phases for Capillary Gas Chromatography

ABSTRACT

A couple of stabilized calix[6]cryptand steroisomers were synthesized by capping 1,3,5-trimethoxy-p-tert-butylcalix[6]arene with 1,1,1-tri(tosyloxyethoxyethoxymethyl)-propane and used as stationary phases for capillary gas chromatography. Their chromatographic characteristics and separation mechanism for aromatic positional isomers and polycyclic aromatic hydrocarbons are discussed.     

A Rapid Method for the Prefractionation of Essential Oils. Application to the Essential oil of Black Spruce [Picea Mariana (Mill.) BSP.]

Abstract

A rapid method for the prefractionation of complex essential oils, prior to the identification of their components, is described. The use of “hybrid” flash chromatography, developed in our laboratories, in a specially constructed, jacketed column, which permits the use of low boiling solvents, makes it possible to effect satisfactory separations through a single column rather than through multiple columns as in classical methods, and in a fraction of the time required. The procedure enables a facile separation of hydrocarbons from oxygenated compounds and yields, in some instances, fractions of pure compounds. Enriched fractions of trace constituents are also obtainable for identification by gas chromatography. The method is rapid and inexpensive.     

Determination of mono- to tetracyclic aromatic hydrocarbons in lubricating oil

Liquid – liquid extraction with N-methyl-2-pyrrolidone, combined with solid-phase extraction on silica gel using n-pentane and dichloromethane as solvents, has been used for the isolation and concentration of the aromatic fraction from lubricating oil. The identification of individual compounds in this aromatic fraction was performed by capillary gas chromatography–mass spectrometry (CGC-MS) and by determination of retention indices. Quantitative results were obtained by flame ionization detection (CGC-FID). Eighty four compounds, predominantly naphthalenes, phenanthrenes, biphenyls, fluorenes, dibenzo-thiophenes, and their alkylated derivatives, have been identified in a commercial lubricating oil. The total amount of the aromatic fraction did not exceed 0.04 % of the oil.     

Quantitative High - Resolution Gas Chromatography and High - Resolution Gas Chromatography/Mass Spectrometry Analyses of Carbonaceous Fine Aerosol Particles

Abstract

Methods have been developed for the quantification of low-microgram levels of the extractable organic matter contained in the atmospheric fine aerosol fraction. Extract quantification is accomplished by computer-assisted high-resolution gas chromatography (HRGC) used in conjunction with a procedural recovery mixture containing perdeuterated compounds of differing polarity and molecular weight. Recovery data for these species indicate that relative volatility rather than functional group classification is the primary factor affecting overall recovery. Routine quality control analysis is performed on a per-sample basis by high-resolution gas chromatography/mass spectrometry (HRGC/MS) for confirmation of the standard components and for identification of procedural contaminants. By the way of illustration, fine aerosol samples have been analyzed from Anaheim. California. The absolute solvent extract yields range from 49 to 346μg of organic carbon, and demonstrate a seasonal variation with winter maximum and summer minimum concentrations.     

Composition and antioxidant activity of the essential oil of Artemisia annua L

Abstract

Artemisia annua L. is an annual Eurasian desert-steppe plant. The composition of essential oils found in Artemisia annua from Russian (Buryatian) flora was analyzed in this work using gas chromatography mass-spectrometry method. Artemisia ketone, β-selinene, caryophyllene, caryophyllene oxide, germacrene D were the main components of the analyzed essential oils. The comparison of own and literature data showed that the essential oils of A. annua conditionally could be divided into “Asian” and “European” groups. Our samples, referring to “Asian” profile, exhibited higher antiradical activity in comparison with data from previously published studies.     

Chemical composition of essential oils of Anthemis secundiramea Biv. subsp. secundiramea (Asteraceae) collected wild in Sicily and their activity on micro-organisms affecting historical art craft

Abstract

In the present study, the chemical composition of the essential oil from the aerial parts of Anthemis secundiramea Biv. subsp. secundiramea L. collected in Sicily was evaluated by GC and gas chromatography–mass spectrometry. The main components of A. secundiramea were (Z)-lyratyl acetate (14.6%), (Z)-chrysanthenyl acetate (9.9%), (Z)-chrysanthenol (8.7%) and (E)-chrysanthenyl acetate (7.7%). The comparing with other studied oils of genus Anthemis belonging to the same clade is discussed. Antibacterial and antifungal activities against some micro-organisms infesting historical art craft, were also determined.     

Proposed Mechanism for Microbial Degradation of Polyacrylate

Abstract

A possible aerobic degradation mechanism for polyacrylate (PA) was examined with acrylic oligomer-utilizing bacteria (Microbacterium sp., Xanthomonas maltophilia, and Acinetobacter sp.), using a model compound (1,3,5-pentane tricarboxylic acid, PTCA). Acyl-coenzyme A synthetase activities were detected with dialyzed cell-free extracts of PTCA-utilizing bacteria toward PTCA, PA 500, and PA 1000. This result suggested that PA is activated by coenzyme A and metabolized via PA-coenzyme A. Metabolic products formed from PTCA were detected in culture filtrates and reaction mixtures of washed cells. Fraction A was detected as a main metabolite by high-performance liquid chromatography. A small amount of fraction B was concomitant with fraction A. Also, another fraction, C, was detected. These intermediate metabolites were characterized by LC-MS as 1,3,5-(1- or 2-pentene)tricarboxylic acid for fractions A and B and as 1,3,5-(2-oxopentane)tricarboxylic acid for fraction C. Fraction A was metabolized far faster than fraction B. Fraction B was thought to be an artifact formed from fraction A under alkaline conditions. Thus PTCA and also PA seemed to be metabolized by the mechanism similar to β-oxidation of fatty acids. The degradation of PTCA by washed cells was slower than that by growing cells and was inhibited by 5 mM NaN₃. This suggests that the metabolism is linked to a respiratory chain of bacteria.     

Synthesis of Selectively Permodified γ–Cyclodextrins. A New Set of Chiral Stationary Phases in Capillary GC

ABSTRACT

Two pairs of new chiral selectors, derived from octakis(6-O-t-butyldimethylsilyl)- and octakis(6-O-t-hexyldimethylsilyl)-γ-cyclodextrin, were synthesized with inverse substitution patterns at the secondary positions. 2-O-methyl-3-O-acetyl- and 2-O-acetyl-3-O-methyl derivatives are suggested as useful models to further investigate the effect of substituents at C-2 and C-3 on the efficiency of enantio-separation using gas chromatography.     

Overview of Analytical Methodologies for Dioxin Analysis

Abstract

Poly(chlorinated) dibenzo‐p‐dioxins and dibenzofurans (PCDDs/PCDFs) are persistent organic pollutants which are globally distributed in practically all environmental compartments and which exert a broad spectrum of toxic and biochemical effects. Humans are exposed to these compounds mainly through the diet with food of animal origin usually being the predominant source.

Multiple step isolation and clean up procedures are necessary to determine trace levels of these analytes in complex environmental and biological samples. This article reviews some of the recent developments in the extraction procedures, such as SFE, PLE, HS‐SPME, MAE, SCWE, ASE; clean‐up areas and instrumental analysis of dioxins in biological/environmental samples. Due to its specificity and sensitivity gas chromatography coupled with high resolution mass spectrometry (GC–HRMS), high‐resolution gas chromatography high‐resolution mass spectrometry (HRGC‐HRMS), or GC‐MS/GC techniques have been extensively applied to environmental, medicinal, and biological studies.     

GC and Mass-Spectrometric Comparison of Organo Sulfur Compounds in Two Varieties of Iranian Garlic

Abstract

Garlic antibiotic action is well known; it is reputed to offer protection against coronary thrombosis and atherosclerosis exhibiting antioxidant and anticancer effects. ^1,2 In this work ¹ H NMR and gas chromatography in conjunction with mass spectrometry have been used for the identification and determination of these compounds in two varieties of Iranian garlic [Allium sativum var. sativum (I) and Allium sativum var. holmense (II)]. The organosulfur compounds in (I) exhibiting a concentration higher than 1% are diallyl sulfide (1.3%), diallyl disulfide (8%), methyl allyl disulfide (19%), methyl allyl trisulfide (3.2%), diallyl trisulfide (5.5%), diallyl tetrasulfide (2%), 2,3-dimethyl thiophen (1.8%), 5-methyl-1,2,3-thiadiazol (5%), and 1,2-ditiolan-3-carboxilic acid (1.5%). The amount of organosulfur compounds in (II) are diallyl disulfide (2%), methyl allyl trisulfide (6.3%), diallyl tetrasulfide (5%), and cyclopentanthiol (2.5%).     

Investigation of antiplasmodial efficacy of lupeol and ursolic acid isolated from Ficus benjamina leaves extract

Abstract

This study emphasizes on the investigation of antiplasmodial activity of triterpenoids isolated from Ficus benjamina leaves. An unsaponified fraction of petroleum ether extract of plant leaves was subjected to silica gel column chromatography which led to the isolation of two known triterpenoids; namely ursolic acid and lupeol. These compounds were evaluated for antiplasmodial activity by schizont maturation inhibition assay using 3D7 Plasmodium strains. Both, ursolic acid and lupeol were found to exhibit significant antiplasmodial effect with an IC₅₀ value of 18?µg/ml and 3.8?µg/ml, respectively. This study further confirms the traditional role of Ficus benjamina plant in the treatment of malaria which may be attributed to ursolic acid and lupeol.