Zwitterionic codeine-derived methacrylate monoliths for enantioselective capillary electrochromatography of chiral acids and chiral bases.

Thiol-ene click reaction of N-acetyl-L-cysteine methyl ester to codeine, followed by reaction with allyl isocyanate and hydrolysis to the corresponding zwitterionic chiral selector and its subsequent bonding to the surface of a methacrylate monolith provided a new chiral capillary column for enantiomer separation of chiral acids and chiral bases. First, the epoxy groups of a poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith were converted into amine residues, followed by reaction with allylglycidyl ether. In this way, a spacer arm was bonded to the surface before coating and cross-linking poly(3-mercaptopropyl methylsiloxane) (PMPMS) via radical addition (thiol-ene click reaction) to the surface. In order to improve the performance of the monolithic chiral stationary phase, thio ether and residual thiol groups were oxidized to sulfonyl and sulphonate groups, respectively. This novel chiral stationary phase (CSP) was evaluated by capillary electrochromatography (CEC) using two chiral model compounds, namely N-3,5-dinitrobenzoyl-R,S-leucine (retained by anion-exchange mechanism) and mefloquine (by cation-exchange process). The ion-exchange retention mechanism on the CSP was characterized for these two counterionic model solutes by varying the mobile phase composition, including the nature of solvents, the concentration of counter-ions and co-ions, and the acid-to-base ratio. A series of chiral ß-blockers and amino acid derivatives was used to further check the performance of the modified monolith under the optimal conditions. Several enantiomers were baseline resolved with reasonable peak efficiencies (up to 60,000 theoretical plates per meter for the second eluted enantiomer).

Application of Organic Monolithic Materials to Enantioseparation in Capillary Separation Techniques.

This review article is primarily focused on the state-of-the-art of enantioseparations on organic monolithic materials. The article gives an overview of the chiral stationary phases and its application in capillary electrochromatography (CEC), and capillary- and nano-liquid chromatography (cLC and nLC). Since thousands of publications have been emerged from 2000's and citing all these papers would extend the scope of this review; then, recent developments from last 10 years (2006 to 2016) will be mentioned. Mostly, stationary phases based on copolymers obtained from chiral functional monomers and surface modifications of organic monoliths with chiral ligands will be discussed. The effective application of these chiral separation methodologies in several analysis areas will be also included.

Determination of the four major surfactant classes in cleaning products by reversed-phase liquid chromatography using serially connected UV and evaporative light-scattering detection.

A method for the simultaneous determination of the most frequently used surfactant families -linear alkyl benzenesulphonates (LAS), alkyl ether sulphates (AES), fatty alcohol ethoxylates (FAE) and oleins (soaps, fatty acid salts) - in cleaning products, has been developed. The common reversed phase octyl (C8), pentafluorophenyl and biphenyl columns were not capable of separating the anionic LAS and AES classes; however, since only LAS absorbs in the UV, these two classes were independently quantified using a C8 column and serially connected UV and ELSD detection. The best compromise to resolve the four surfactant classes and the oligomers within the classes was achieved with a C8 column and an ACN/water gradient. To enhance retention of the anionic surfactants, ammonium acetate, as an ion-pairing agent compatible with ELSD detection, was used. Also, to shift the olein peaks with respect to that of the FAE oligomers, acetic acid was used. In the optimized method, modulation of the mobile phase, using ammonium acetate during elution of LAS and AES, and acetic acid after elution of LAS and AES, was provided. Quantitation of the overlapped LAS and AES classes was achieved by using the UV detector to quantitate LAS and the ELSD to determine AES by difference. Accuracy in the determination of AES was achieved by using a quadratic model, and by correcting the predicted AES concentration according to the LAS concentration previously established using the UV chromatogram. Another approach also leading to accurate predictions of the AES concentration was to increase the AES concentrations in the samples by adding a standard solution. In the samples reinforced with AES, correction of the predicted AES concentration was not required. FAE and olein were quantified using also quadratic calibration.

Thermal desorption gas chromatography with mass spectrometry study of outgassing from polymethacrylimide foam (Rohacell®).

Polymethacrylimide foams are used as light structural materials in outer-space devices; however, the foam closed cells contain volatile compounds that are outgassed even at low temperatures. These compounds ignite as plasmas under outer-space radiation and the intense radio-frequency fields used in communications. Since plasmas may cause spacecraft fatal events, the conditions in which they are ignited should be investigated. Therefore, qualitative and quantitative knowledge about polymethacrylimide foam outgassing should be established. Using thermogravimetric analysis, weight losses reached 3% at ca. 200°C. Thermal desorption gas chromatography with mass spectrometry detection was used to study the offgassed compounds. Using successive 4 min heating cycles at 125°C, each one corresponding to an injection, significant amounts of nitrogen (25.3%), water (2.6%), isobutylene (11.3%), tert-butanol (2.9%), 1-propanol (11.9%), hexane (25.3%), propyl methacrylate (1.4%), higher hydrocarbons (11.3%), fatty acids (2.2%) and their esters (1.3%), and other compounds were outgassed. Other compounds were observed during the main stage of thermal destruction (220-280°C). A similar study at 175°C revealed the extreme difficulty in fully outgassing polar compounds from polymethacrylimide foams by baking and showed the different compositions of the offgassed atmosphere that can be expected in the long term.

Hybrid methacrylate monolithic columns containing magnetic nanoparticles for capillary electrochromatography.

Vinylized iron oxide magnetic nanoparticles (VMNPs) were incorporated into polymethacrylate monolithic columns to develop novel stationary phases with enhanced separation performance. The VMNPs were dispersed in a polymerization mixture containing gycidyl methacrylate and ethylene glycol dimethacrylate as monomers, cyclohexanol and 1-dodecanol as porogens and azobisisobutyronitrile as initiator. The stability of the VMNPs in the polymerization mixture was investigated at several VMNP contents. Using short UV-polymerization times, polymeric beds with homogenously dispersed VMNPs were obtained. The novel stationary phases were characterized by scanning electron microscopy. The chromatographic performance of these hybrid monoliths was evaluated using alkyl benzenes and organophosphorous pesticides as test solutes. Using capillary electrochromatography, efficiencies up to 130,000 plates/m were achieved. The increase of the specific surface area of hybrid monoliths led to an increase in the retention of all the test analytes, and an enhancement of efficiency. The resulting hybrid monolithic columns exhibited satisfactory column to-column and batch-to-batch reproducibilities with RSDs values below 6%.

Sensitive determination of parabens in human urine and serum using methacrylate monoliths and reversed-phase capillary liquid chromatography-mass spectrometry.

A method for the determination of parabens in human urine and serum by capillary liquid chromatography (cLC) with UV-Vis and mass spectrometry (MS) detection using methacrylate ester-based monolithic columns has been developed. The influence of composition of polymerization mixture was studied. The optimum monolith was obtained with butyl methacrylate monomer at 60/40% (wt/wt) butyl methacrylate/ethylene dimethacrylate ratio and 50wt% porogens (composed of 36wt% of 1,4-butanediol, 54wt% 1-propanol and 10wt% water). Baseline resolution of analytes was achieved through a mobile phase of acetonitrile/water in gradient elution mode. Additionally, dispersive liquid-liquid microextraction (DLLME) was combined with both cLC-UV-Vis and cLC-MS to achieve the determination of parabens in human urine and serum samples with very low limits of detection. Satisfactory intra- and inter-day repeatabilities were obtained in UV-Vis and MS detection, although the latter provided lower detection limits (up to 300-fold) than the UV-Vis detection. Recoveries for the target analytes from spiked biological samples ranged from 95.2% to 106.7%. The proposed methodology for the ultra-low determination of parabens in human urine and serum samples is simple and fast, the consumption of reagents is very low, and very small samples can be analyzed.

Evaluation of 2,3-epoxypropyl groups and functionalization yield in glycidyl methacrylate monoliths using gas chromatography.

Poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) is most frequently used as parent monolith to obtain stationary phases with a variety of surface chemistries for liquid chromatography and capillary electrochromatography. Functionalization is performed by opening the accessible 2,3-epoxypropyl groups of the monolith with a suitable reagent. The number of 2,3-epoxypropyl groups which are accessible before and after the functionalization reaction, and the grafting yield, are important parameters, required both to optimize functionalization and to interpret the chromatographic performance of functionalized monoliths. In this work, a method capable of providing this information for parent and functionalized poly(GMA-co-EDMA) monoliths prepared both in silica capillaries and in other supports is proposed. First, sulfuric acid and lithium aluminium hydride (LiAlH4) are sequentially used to release the 2,3-epoxypropyl groups as glycerol, which is subsequently determined by GC. About 6.0mmol of 2,3-epoxypropyl groups per gram of monolith was found in this work for the parent monoliths prepared in silica capillaries using UV-initiation. The monoliths were also functionalized using ammonia (NH3), diethylamine (DEA) and epinephrine, and the amount of residual 2,3-epoxypropyl groups, and hence the functionalization yield, were established by also measuring the GC peak of glycerol. The amounts of 2,3-epoxypropyl groups and the derivatization yields were established with RSDs of 1.7 and 3.4%, respectively. The proposed method was also applied to the characterization of poly(GMA-co-EDMA) monoliths prepared in glass vials. Significant differences with respect to those prepared in 100µm I.D. silica capillaries were evidenced.

Polymethacrylate monoliths with immobilized poly-3-mercaptopropyl methylsiloxane film for high-coverage surface functionalization by thiol-ene click reaction.

In this work, new polythiol-functionalized macroporous monolithic polymethacrylate-polysiloxane composite materials are presented which can be useful substrates for highly efficient immobilization of (chiral) catalysts, chromatographic ligands, and other functional moieties by thiol-ene click reaction. Poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) monoliths were coated with a poly-3-mercaptopropyl methylsiloxane (PMPMS) film and subsequently the polymer was covalently immobilized by formation of crosslinks via nucleophilic substitution reaction with pendent 2,3-epoxypropyl groups on the monolith surface. This monolith, though, showed similar levels of surface coverage as a reference monolith obtained by opening of the epoxide groups with sodium hydrogen sulfide. However, a 3-step functionalization by amination of the epoxy monolith, followed by its vinylation with allylglycidyl ether and subsequent thiolation by coating of a thin polythiol (PMPMS) film and crosslinking by click reaction furnished a monolith with more than 2-fold elevated thiol coverage. Its further functionalization with a clickable chiral quinine carbamate selector clearly documented the benefit of highly dense thiol surfaces for such reactions and synthesis of functional materials with proper ligand loadings. The new monoliths were chromatographically tested in capillary electrochromatography mode using N-3,5-dinitrobenzoyl-leucine as chiral probe and the capillary column with the monolith having the highest selector coverage, produced from the precursor with the most thiols on the surface, showed the largest separation factor. By performic acid oxidation the surface characteristic could be tuned and strongly altered due to a delicate balance of enantioselective and non-specific interactions.

UV-polymerized butyl methacrylate monoliths with embedded carboxylic single-walled carbon nanotubes for CEC applications.

The preparation of polymeric monoliths with embedded carboxy-modified single-walled carbon nanotubes (c-SWNTs) and their use for capillary electrochromatography (CEC) is described. Carbon nanotube composites were obtained by preparing a polymerization mixture in the presence of increasing c-SWNT concentrations, followed by UV initiation. The novel stationary phases were studied by optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Using short UV-polymerization times, the optimized porogenic solvent (a binary mixture of 1,4-butanediol and 2-propanol) gave rise to polymeric beds with homogenously dispersed embedded c-SWNTs. The CEC features of these monoliths were evaluated using polycyclic aromatic hydrocarbons (PAHs), non-steroidal anti-inflammatory drugs (NSAIDs) and chiral compounds. The monolith prepared in the presence of c-SWNTs showed enhanced resolution of the text mixtures, including a remarkable capability to separate enantiomers.

Chemical analysis and antioxidant activity of the essential oils of three Piperaceae species growing in the central region of Cuba.

The present study describes the phytochemical profile and antioxidant activity of the essential oils of three Piperaceae species collected in the central region of Cuba. The essential oils of Piper aduncum, P. auritum and P. umbellatum leaves, obtained by hydrodistillation, were analyzed by gas chromatography-mass spectrometry. The main components of P. aduncum oil were piperitone (34%), camphor (17.1%), camphene (10.9%), 1,8-cineol (8.7%) and viridiflorol (7.4%), whereas that of P. auritum and P. umbellatum was safrole (71.8 and 26.4%, respectively). The antioxidant properties of the essential oils were also evaluated using several assays for radical scavenging ability (DPPH test and reducing power) and inhibition of lipid oxidation (ferric thiocyanate method and evaluation against Cucurbita seed oil by peroxide, thiobarbituric acid and p-anisidine methods). P. auritum showed the strongest antioxidant activity among the Piper species investigated, but lower than those of butylated hydroxyanisol and propyl gallate.

Synchronized gradient elution in capillary liquid chromatography.

The synchronization of injection valve operation and gradient elution in capillary liquid chromatography (cHPLC) is studied. Focus is placed on the cHPLC systems which rely on the splitting of a primary flow to provide the much smaller secondary flow required at the injection device and analytical column. Owing to the tiny secondary flow rates, synchronization is necessary to achieve proper optimization of gradient elution methods. Otherwise, there is a risk of having the analytes totally or partially eluted in the initial isocratic conditions, and there is no control on the actual gradient profile reaching the column. Synchronization is first achieved by switching back the valve to bypass after injection. This is important to save time, and to avoid the gradient slope to be reduced by mixing within the internal volume of the injector (a 47% of slope reduction, in the conditions used in this work). Valve switching to bypass should be produced immediately after the arrival of the end of the sample plug to the valve (tV). Fine system synchronization is further achieved by starting the gradient at the match time (tM), which is the time required to match the arrival of both the gradient front and the end of the sample plug to the valve, and therefore also to the column inlet. Synchronization of these two events requires starting the gradient either before or even after the injection, thus to prevent a late or an early arrival of the gradient front to the injection valve, respectively. Owing to their dependence with the backpressure, both tV and tM should be measured in the presence of the column at the initial gradient conditions. Simple experiments designed to measure tV and tM are described. With synchronization according to the techniques described in this work, control on the real gradient elution conditions at the column location is maintained, the analysis time is reduced and efficiency improves. The effects of synchronization are illustrated by injecting a mixture of alkylbenzenes. At 1µL min(-1), valve switching to bypass reduced analysis time from ca. 36 to 12min (butylbenzene), and improved peak symmetry (from 2.00 to 0.94 for methylbenzene) and efficiency (the average apparent plate count increased approximately 60%). Synchronization according to the match time further improved efficiency (approximately, up to 120%).

Determination of alcohols in essential oils by liquid chromatography with ultraviolet detection after chromogenic derivatization.

An HPLC-UV method to determine compounds having a hydroxyl functional group in plant essential oils is developed. The sample is diluted with 1,4-dioxane and the analytes are derivatized with phthalic anhydride. The derivatives (phthalates hemiesters) are separated on a C8 column using an acetonitrile (ACN)/water gradient. Separation conditions were optimized using the DryLab(®) method development software. For the alcohols and phenols present in mint and rose essential oils, optimization led to a ca. 40min gradient time and a column temperature of 8°C. The alcohol and its derivatives were identified using HPLC with mass spectrometry (MS) detection. A large sensitivity enhancement was obtained by derivatization protocol. The HPLC-UV method was compared to GC with flame ionization detector (FID) and GC-MS. The limits of detection (LODs) obtained by the proposed method were better than those obtained by GC-FID and of the same order as those achieved by GC-MS. The three methods were satisfactorily applied to the determination of alcohols in essential oils. Therefore, the recommended method is of interest as an alternative to GC methods, to investigate the presence of compounds having an alcohol group at low concentrations in essential oils.

Methacrylate monolithic columns functionalized with epinephrine for capillary electrochromatography applications.

Epinephrine-bonded polymeric monoliths for capillary electrochromatography (CEC) were developed by nucleophilic substitution reaction of epoxide groups of poly(glycidyl-methacrylate-co-ethylenedimethacrylate) (poly(GMA-co-EDMA)) monoliths using epinephrine as nucleophilic reagent. The ring opening reaction under dynamic conditions was optimized. Successful chemical modification of the monolith surface was ascertained by in situ Raman spectroscopy characterization. In addition, the amount of epinephrine groups that was bound to the monolith surface was evaluated by oxidation of the catechol groups with Ce(IV), followed by spectrophotometric measurement of unreacted Ce(IV). About 9% of all theoretical epoxide groups of the parent monolith were bonded to epinephrine. The chromatographic behavior of the epinephrine-bonded monolith in CEC conditions was assessed with test mixtures of alkyl benzenes, aniline derivatives and substituted phenols. In comparison to the poly(GMA-co-EDMA) monoliths, the epinephrine-bonded monoliths exhibited a much higher retention and slight differences in selectivity. The epinephrine-bonded monolith was further modified by oxidation with a Ce(IV) solution and compared with the epinephrine-bonded monoliths. The resulting monolithic stationary phases were evaluated in terms of reproducibility, giving RSD values below 9% in the parameters investigated.

Preparation and evaluation of lauryl methacrylate monoliths with embedded silver nanoparticles for capillary electrochromatography.

In this article, capillary columns constituted by lauryl methacrylate monoliths with embedded silver nanoparticles (AgNPs) were developed and tested. Two incorporation approaches of AgNPs in monoliths were explored. The AgNPs were either photogenerated in situ during polymerization of the monolith by UV irradiation, or incorporated to the polymerization mixture (ex situ). The influence of the AgNP concentration on the morphological and chromatographic properties of the polymer matrix was investigated, and both the in situ and ex situ approaches were comparatively discussed. The morphology of the monoliths was characterized by electron microscopic techniques, and their electrochromatographic performance was also evaluated with test mixtures of neutral compounds (sterols, fatty acid methyl esters, tocopherols, and polyaromatic hydrocarbons).

γ-Oryzanol and tocopherol contents in residues of rice bran oil refining.

Rice bran oil (RBO) contains significant amounts of the natural antioxidants γ-oryzanol and tocopherols, which are lost to a large degree during oil refining. This results in a number of industrial residues with high contents of these phytochemicals. With the aim of supporting the development of profitable industrial procedures for γ-oryzanol and tocopherol recovery, the contents of these phytochemicals in all the residues produced during RBO refining were evaluated. The samples included residues from the degumming, soap precipitation, bleaching earth filtering, dewaxing and deodorisation distillation steps. The highest phytochemical concentrations were found in the precipitated soap for γ-oryzanol (14.2 mg g(-1), representing 95.3% of total γ-oryzanol in crude RBO), and in the deodorisation distillate for tocopherols (576 mg 100 g(-1), representing 6.7% of total tocopherols in crude RBO). Therefore, among the residues of RBO processing, the deodorisation distillate was the best source of tocopherols. As the soap is further processed for the recovery of fatty acids, samples taken from every step of this secondary process, including hydrosoluble fraction, hydrolysed soap, distillation residue and purified fatty acid fraction, were also analyzed. The distillation residue left after fatty acid recovery from soap was found to be the best source of γ-oryzanol (43.1 mg g(-1), representing 11.5% of total γ-oryzanol in crude RBO).

Chemical composition, antioxidant properties and antimicrobial activity of the essential oil of Murraya paniculata leaves from the mountains of Central Cuba.

The essential oil of Murraya paniculata L leaves from the mountains of the Central Region of Cuba, obtained by hydrodistillation, was analyzed by gas chromatography-mass spectrometry. Eighteen compounds, accounting for 95.1% of the oil were identified. The major component was beta-caryophyllene (ca. 30%). The antioxidant activity of essential oil was evaluated against Cucurbita seed oil by peroxide, thiobarbituric acid and p-anisidine methods. The essential oil showed stronger antioxidant activity than that of butylated hydroxyanisole and butylated hydroxytoluene, but lower than that of propyl gallate. Moreover, this antioxidant activity was supported by the complementary antioxidant assay in the linoleic acid system and 2, 2'-diphenyl-1-picrylhydrazyl. The essential oil also showed good to moderate inhibitory effects against Klebsiellapneumoniae and Bacillus subtilis.

Sensitive determination of polycyclic aromatic hydrocarbons in water samples using monolithic capillary solid-phase extraction and on-line thermal desorption prior to gas chromatography-mass spectrometry.

A methacrylate-based monolithic capillary column has been evaluated for the preconcentration of polycyclic aromatic hydrocarbons (PAHs) from environmental water samples. For this purpose, the monolyte was in situ synthesized in a 6cm×0.32mm id fused-silica capillary. The microextraction unit was fitted to a micro-HPLC pump to pass 10mL of sample. The isolated pollutants were eluted by means of 10µL of methanol, the organic phase being directly collected in a specific interface that can be fitted to the injection port of the gas chromatograph without modification. The interface allows the on-line thermal desorption of the PAHs, avoiding the dilution and providing enough sensitivity to reach the legal limits established for these pollutants in the matrices selected. The limits of detection achieved for 10mL of water ranged between 2.8ng/L (indeno(1,2,3-cd)pyrene) and 11.5ng/L (acenaphthene) with acceptable precision (between 4.5 and 18.2% RSD). The method was applied to the determination of the selected PAHs in tap, river waters and sewage, being fluoranthene and pyrene detected in all of them at concentrations lower than the legal limits established for these compounds in the matrices assayed.

Evaluation of molecular mass and tacticity of polyvinyl alcohol by non-equilibrium capillary electrophoresis of equilibrium mixtures of a polymer and a dye.

Non-equilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) has been used to characterize polyvinyl alcohol (PVA). Commercial PVA samples with different molecular masses, from M(w)=15 up to 205 kDa, were used. According to the (13)C NMR spectra, the samples also differed in tacticity (stereoregularity). Mixtures of PVA and the anionic azo-dye Congo Red (CR) were injected in the presence of a borate buffer. The electropherograms gave a band and a peak due to the residual PVA-CR complex and the excess dye, respectively, plus a superimposed exponential decay due to the partial dissociation of the complex during migration. The stoichiometry of the PVA-CR complex, q=[monomer]/[dye], reached a maximum, q(sat), which depended on both M(w) and tacticity of PVA. Thus, q(sat) decreased from a molar ratio of ca. 4.9 to 3.6 at increasing M(w) values, this variation also being largely dependent on tacticity. A similar dependence of the electrophoretic mobility of the complex on both M(w) and tacticity was also observed. A possible explanation, based on the formation of a stack of CR ions inside the PVA-CR complex, was proposed and discussed. Finally, at increasing M(w) values, the stability constant of the complex increased slightly, and the pseudo-first order dissociation rate of the complex decreased, this later parameter also showing a dependence on both M(w) and tacticity.

Classification of pumpkin seed oils according to their species and genetic variety by attenuated total reflection Fourier-transform infrared spectroscopy.

Attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR), followed by multivariate treatment of the spectral data, was used to classify seed oils of the genus Cucurbita (pumpkins) according to their species as C. maxima, C. pepo, and C. moschata. Also, C. moschata seed oils were classified according to their genetic variety as RG, Inivit C-88, and Inivit C-2000. Up to 23 wavelength regions were selected on the spectra, each region corresponding to a peak or shoulder. The normalized absorbance peak areas within these regions were used as predictors. Using linear discriminant analysis (LDA), an excellent resolution among all categories concerning both Cucurbita species and C. moschata varieties was achieved. The proposed method was straightforward and quick and can be easily implemented. Quality control of pumpkin seed oils is important because Cucurbita species and genetic variety are both related to the pharmaceutical properties of the oils.

Chromium(VI) oxide oxidation of non-ethoxylated and ethoxylated alcohols for determination by electrospray ionization mass spectrometry.

A new derivatization procedure to increase the sensitivity of electrospray ionization mass spectrometry (ESI-MS) to non-ethoxylated and ethoxylated alcohols was investigated. The analytes were oxidized with chromium(VI) oxide and the resulting carboxylic and ethoxy-carboxylic acids were isolated by extraction with ethyl acetate; the extracts were alkalinized and infused into the ESI-MS system working in the negative-ion mode. The yields of the combined oxidation-extraction were ca. 100% for non-ethoxylated fatty alcohols dissolved in acetone and they decreased moderately in samples containing increasing amounts of water (e.g., a 75% yield was obtained with 50% water). Ethoxylated alcohols with more than two ethylene oxide units resulted in yields of ca. 60%. Low limits of detection (LODs) were obtained when the procedure was applied to the analysis of body-care products and cosmetics containing fatty alcohols, e.g., in a varicose-vein cream, the LODs were 25 microg cetyl alcohol and 7.5 microg stearyl alcohol (detected as palmitic acid and stearic acid, respectively) per gram of sample. High molecular mass alcohols were also detected in seawater after pre-concentration by solid-phase extraction. Thus, the proposed method is particularly valuable for use in industrial samples having complex matrices and in environmental samples and it is competitive with other methods for the analysis of trace amounts of fatty alcohols.