Review

Received: 2 October 2008, Accepted: 6 October 2008 Published online in Wiley Interscience

(www.interscience.wiley.com) DOI 10.1002/bmc.1168

Carbon-based sorbents in chromatography. New achievements

John Wiley & Sons, Ltd.

T. Cserhti*
Carbon-based sorbents in chromatography

ABSTRACT: The newest results in the employment of carbon-based composites in various chromatographic techniques such as gasliquid chromatography, high-performance liquid chromatography and electrically driven separation techniques for the separation, quantitative determination and identification of a wide variety of compounds in complicated matrices are compiled. The results are concisely described and critically evaluated. The future trends in the application of carbon-based compounds in the chromatographic separation methods are briefly discussed. Copyright 2008 John Wiley & Sons, Ltd. Keywords: carbon-based supports; gasliquid chromatography; high-performance liquid chromatography; electrically driven systems. deoxyguanosine a biomarker of glyoxal exposure. After enrichment the samples were analyzed by HPLC using a diol column and electrospray mass spectrometric detection (Olsen et al., 2008). The beneficial biological effect of extracts containing natural antioxidants such as carnosic acid and rosmarinic acid promoted the development of preconcentration methods for their enrichment. Thus, the extractionadsorptiondesorption process under supercritical conditions was studied in detail. Oleoresin extracted from rosemary (Rosemarinus officinalis) by organic solvents was reextracted under supercirical conditions and further cleaned up using various absorbents such as activated carbon, silica gel, magnesium silicate and activated clay. The amount of carnosic acid and rosmarinic acid was assesed using a HPLC-UVvis detector system with an octadecyl silica (ODS) column. The investigations

Introduction
Because of their advantageous adsorption characteristics, carbon sorbents prepared by various synthetic procedures and sometimes mixed with other solids are extensively used in chromatographic separation techniques for the preconcentration, prepurification and cleaning of the molecules of interest, even for the improvement of their separation. The number of carbon-based solids employed in chromatographic separation methods is fairly high; some of them are commercial products; others were synthesized in different research laboratories for special separation purposes. The rational application of carbon-based adsorbents offers an excellent possibility for the analysis of a considerable number of solutes by increasing the reliability, sensitivity and reproducibility of any chromatographic method. Carbon adsorbents can be successfully employed in many fields of research and development such as pharmaceutical and food analysis, biochemical and biophysical research and health care. The objectives of the review are the compilation and evaluation of the newest results in the chromatographic application of carbonbased adsorbents and the critical discussion of the results.

* Correspondence to: T. Cserhti, Research Institute of Materials and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences, PO Boksz 17, 1525 Budapest, Hungary. E-mail: tevi@chemres.hu Research Institute of Materials and Environmental Chemistry, Chemical Research Center, Hungarian Academy of Sciences, Budapest, Hungary Abbreviations used: ACN, acetonitrile; CAR/PDMS, carboxen/polydimethylsiloxane; CE, capillary electrophoresis; CI-MS/MS, chemical ionization tandem mass spectrometry; CNs, carbon nanotubes; d.w., dry weight; EKC, electrokinetic chromatograhpy; FID, flame ionization detector; FTD, flame thermoionic detector; GAC, granular activated carbon; GC, gas-chromatography; GCB, graphitized carbon black; HS-SPME; headspace solid-phase microextraction; IC, ion chromatography; IGC, inverse gas chromatography; ILC, inverse liquid chromatography; MAE, microwave-assisted extraction; MDMA,3,4methylnedioximetham-phetamine; MEKC, micellar electrokinetic capillary chromatography; MWCNTs, multi-wall carbon nanotubes; MWNTs, multiwall nanotubes; ODS, octadecyl silica; OTA, ochratoxin A; PA, polyacrylate; PAH, polycyclic aromatic hydrocarbons; PCB, polychlorinated biphenyl; PCN, polychlorinated naphthalenes; PDMS, polydimethylsiloxane; PDMS/ DVB, carboxen/polydimethylsioxane; PEI, polyethyleneimine; PGC, porous graphitized carbon; PSA, primary secondary amine, RSD, relative standard deviation; SCCP, short-chain chlorinated paraffins; SFC, supercritical fluid chromatography; SPE, solid-phase extraction; -SPE, micro-solid-phase extraction; SPME, solid-phase microextraction; SWNTs, single wall carbon nanotubes; TD, thermal desorption; THI, 2-acetyl-4-(1,2,3,4-tetrahydroxybutyl)imidazole; TLC, thin layer chromatography; VOCs, volatile organic compounds; VOSCs, volatile organic sulfur compounds.

Carbon-based adsorbents
Health Care The thiocyanate and iodide concentrations were determined in powdered milk and infant formula using on-line enrichment ion chromatography with photodiode array detection. Samples were ultrafiltrated then preconcentrated on carbon solid-phase extraction (SPE). The limit of quantitation (LOQ) values of thiocyanate and iodide in infant formula were 0.2 and 0.04 mg/kg, respectively. The LOQ values in dry milk samples were 1 and 0.2 mg/kg (Niemann and Anderson, 2008). The adsorption capacities of various carbon adsorbents were compared using 1-phenylethylamine and 3,4-methylenedioxymethamphetamine (MDMA, a psychoactive component of ectasy tables), and marked differences were observed in the adsorption capacity of carbon sorbents (Kochana et al., 2008). A trap column (5 1 mm i.d.) filled with Hypercarb (PGC) sorbent was applied for the preconcentration of the adduct glyoxal-

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T. Cserhti indicated that the adsorption efficacy of the carbon adsorbent was the highest (Braida et al., 2007). Activated carbon and sodium bentonate were employed for the reduction of the concentration of the toxin ochratoxin A (OTA) in white wines and phosphate-buffered saline. The efficacy of the removal of OTA was followed by HPLC using an ODS column of 250 4.6 mm. The mobile phase consisted of acetonitrile (ACN) wateracetic acid (47:51:2, v/v/v). It was found that activated carbon readily adsorbs OTA while the efficacy of sodium bentonite was fairly low (Var et al., 2008). Environmental protection Because of their high adsorption capacity, graphite fibers have been employed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in soil. Fluorene, phenanthrene, anthracene, fluoranthene and pyrene were extracted by microwave-assisted extraction (MAE) and adsorbed on graphite fibers (-SPE). Analytes were separated and quantitavely determined by GC-FID and GC-MS. It was found that the limit of detection (LOD) values for GC-FID and GC-MS varied between 2.23.6 and 0.0170.0057 ng/g, respectively. Because of the sensitivity and good separation efficacy, the method was proposed for the quantitative determination of these PAHs in river and marine sediments (Xu and Lee, 2008). Microporous activated carbons were prepared from the chemical activation of Kraft lignin and they were sprinkled onto self-heated alumina substrates. The capacity of these carbons to adsorb benzene was checked by GC-MS and it was compared with the adsorption capacity of commercial carbon black. The measurements indicated that the performance of the new microporous activated carbonbased preconcentrators was superior to that of commercial carbon black (Blanco et al., 2008). A GC-ion trap MS method was developed for the determination of the residues of 12 insecticides (acrinathrin, bifenthrin, carbofuran, cyfluthrin, -cyhalothrin, chlorfenvinphos, deltamethrin, esfenvalerate, fenamiphos, methiocarb and -fluvalinate) and 11 fungicides (cyprodinil, fludioxonil, iprodione, metalaxyl, penconazole, pyrimethanil, procymidone, tebucanozole, triadimefon, triadimenol and vinclozolin) in leafy vegetables. Samples were extracted with ACN and the solute was cleaned-up with graphitized carbon black (GCB)/primary secondary amine (PSA) SPE cartridges. It was established that the RSD value of the method was always lower than 10% and the LOD values were lower than the maximum residue levels determined by the European Regulation (Rosa et al., 2008). A similar preconcentration method was employed for the analysis of pesticide residues in vegetables, fruit and cereals. Pesticides were extracted with ACN and the extract was cleaned up on GCB/PSA cartridges. Residues were separated by LC/MS/ MS and the RSD was <20%. Because of the good separation capacity, the method was proposed for the determination of pesticide residues in agricultural products (Takatori et al., 2008). The application of GC-CI-MS/MS for the determination of sixteen triazine herbicides in soil has also been reported. The ACN extract was cleaned up with home-made graphite carbon black (Zhang et al., 2008). Comprehensive two-dimensional GCtime of flight mass spectrometry was employed for the analysis of 17 polychlorinated dibenzo-p-dioxins/dibenzofurans and 4-non-orthopolychlorinated biphenyl in fish oil. The clean-up of samples was achieved using gel permeation chromatography and GCB adsorption. The limit of quantitation varied between 0.019 and 7.8 pg/g toxic equivalent. The method was proposed for the monitoring of the contamination of fish oils with dioxin and dioxin-like polychlorinated biphenyl (PCB)s (Hoh et al., 2008). The good adsorption capacity of granular-activated carbon (GAC) has been exploited in the removal of dissolved organic matter before the reverse-osmosis of membrane bioreactor effluents. The efficacy of the adsorption step was followed by hydrophobic interaction chromatography. The measurements indicated that about 8090% of the dissolved organic matter can be removed by using GAC (Gur-Reznik et al., 2008). An activated coconut-shell charcoal was employed for the preconcentration of airborne 4-vinyl-1-cyclohexene. The analyte was removed from the charcoal by carbon disulfide and quantitatively determined by GC-FID. It was found that the LOD was 0.044 ng, the recovery was 96.78102.87% with an RSD of 0.34 1.92% (Kongtip et al., 2008). Not only coconut-shell charcoal but also bamboo charcoal was employed for the preconcentration of analytes before the chromatographic separation process. Thus, water samples containing dimethylphthalate, diethyl phthalate, butyl-benzyl phthalate and di-n-butyl phthalate were passed through a cartridge containing bamboo charcoal. Analytes were removed by acetone and separated by HPLC-UV. Bamboo charcoal was proposed for the enrichment of phthalate esters from environmental waters (Zhao et al., 2008). Phthalates (dimethyl-phthalate, diethyl-phthalate and di-nphthalate) were also determined in vegetables using Florisil as dispersant, GCB as purificant and ethyl acetate as eluting agent. Analytes were separated by HPLC coupled with electrospray ionization mass spectrometry. Recoveries varied between 82.7 and 105.7% with RDS values of 1.76.1%. The LOD was 0.988 0.702 ng (Wang et al., 2007a). Volatile organic sulfur compounds (ethyl mercaptan, dimethyl sulfide, carbon disulfide, propyl mercaptan, butyl mercaptan, dimethyl disulfide and 1-pentanethiol) were separated and quantitatively determined in the air at a sewage management area. Analytes were adsorbed in steel tubes containing Tenax TA and Unicarb multisorbent. After thermal desorption (TD) the analytes were investigated by GC-MS. It was established that the recovery and the repeatabilty of the method was good for each compound and its application for the analysis of VOSCs was proposed (Ras et al., 2008). A combined chromatographic method was developed and employed for the separation and quantitative determination of polychlorinated naphthalenes (PCN), polychlorinated biphenyls (PCB) and short-chain chlorinated paraffins (SCCP) in marine sediments. Soxhlet extraction followed by enrichment on Florisil and graphitized carbon cartridges was applied for sample cleanup. GC methods coupled with ion-trap tandem mass spectrometry and with MS in electron capture negative ionization mode were used for the measurement of the concentration of these environmental pollutants. The LOD values were 0.0010.003 ng/ g dry weight for PCNs, 0.211.17 pg/g d.w. for SCCPs and 2.33 44.00 ng/g d.w. for PCBs (Castells et al., 2008). Other Applications Activated carbon prepared from waste apricots was successfully used as adsorbent for the preseparation of butter oil triglycerides from -carotene before alumina column chromatography (Karabulut et al., 2008). Adsorption GC was applied for the investigation of the adsorption of adamantane derivatives to GCB, and the physicochemical

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Carbon-based sorbents in chromatography and structural parameters influencing the adsorption procedures were determined. It was found that that the adsorption potential markedly depended on the cyclohexane fragment (Yashkin et al., 2008). ture range 260340C and was not influenced by the exposure to hexane, dichloromethane, acetone and methanol. The new coating was successfully employed for the GC-FTD determination of organophosphorous pesticides (fenchlorphos, pirimiphosmethyl, chlorpyrophos, ethiom and quinalphos) in water. It was concluded from the data that the new material shows good extraction capacities and is more resistant to extreme temperatures and to the exposure of organic solvents (Zeng et al., 2008). Organophosphorous pesticides were also determined in tomatoes. The performance of circulating cooling-SPME (heating the sample while cooling the fiber coating) was compared with that of traditional SPME. Analytes were separated using a GC-nitrogen phosphorous detector (NPD). It was established that the extraction capacity of activated carbon fiber was higher than that of commercial fibers. RSD values were 5.68.5%, and recoveries 82.590.0%. Because of the good validation parameters, the method was prepared for the determination of organophosphorous pesticides in tomatoes (Chai et al., 2008). A home-made porous-layer activated charcoal fused silica fiber was employed for the SPME clean-up of various organic compounds present in Zataria multiflora Boiss. The optimal SPME conditions were desorption time 2 min; extraction temperature 25C; sample mass 200 mg; and extraction time 25 min. Analytes (thymol, cravacrol, p-cymene, linalool, caryophyllene and terpineol) were well separated and quantitated by GC-MS, the RSD being always lower than 15% (Abkenar et al., 2008). Headspace-solid-phase microextraction using DVB-CAR/PDMS fiber was employed for the preconcentration of volatile organic compounds (VOCs) emitted by wax objects in museums. The samples were analyzed by GC-MS. The method allowed the separation and identification of n-alkanes from C10 to C21, saturated carboxylic acids (C6-C12), benzene and cinnamic acid derivatives (Lattuati-Derieux et al., 2008).

Solid-phase Extraction and Solid-phase Microextraction

Because of their advantageous characteristics (high adsorption capacity, good thermal stability, wide pH range of application), carbon preparations have been employed in the up-to-date extraction technologies such as SPE and solid-phase microextraction (SPME). Thus, various carbon derivatives have been frequently applied as SPE adsorbents for the preconcentration and prepurification of a wide variety of analytes such as pharmaceuticals, pesticides residues, volatile organic compounds, polycyclic aromatic hydrocarbons and polyhalogenated biphenyls. In the majority of cases the analysts use more than one type of SPE adsorbent under different experimental conditions and select the best adsorbent working under optimal conditions. In traditional SPE the liquid sample containing the analytes and the impurities is passed through a cartridge filled with the solid adsorbent. Because of the strong attractive forces between the analytes and the sorbent, the analytes are retained in the cartridge. The cartridge is washed and then the analytes are removed using a small volume of organic solvent. The analytes are concentrated in the relatively small volume of clean solvent and ready for chromatographic separation without further prepurification steps. A considerable number of chromatographic methods using SPE technique have been described. Thus, SPE cartridges filled with multi-wall carbon nanotubes (MWCNTs) were applied for the preconcentration of pesticides residues form environmental waters. The analytes were subsequently separated by HPLC (El-Seikh et al., 2007). Another study indicated that primary and secondary amine/carbon adsorbents were suitable for the enrichment of polar pesticides from food extracts (He and Liu, 2007). Similar results were achieved using SPE extraction dual-layer carbon/PSA adsorbent (Shimelis et al., 2007). SPE employing MWCNTs was successfully applied for the preconcentration of pesticides from water prior GC-MS analysis (Wang et al., 2007b) and for the extraction of fungicides and promethryin from water (Zhou et al., 2007). A pesticide residue determination was developed using extraction with 1% acetic acid in ACN, followed by SPE comparing the efficacy of various adsorbents (neutral alumina, carbon black/ primarysecondary amine, ODS, Florisil, Oasis MCX, and a strong anion exchanger). The preconcentrated samples were analyzed by GC-MS. The measurement indicated that only neutral alumina was suitable for the remove of impurities influencing the GC determination of pesticides (Jeong et al., 2008). Similarly to SPE, the SPME technique also employs a solid adsorbent for the prepurification and preconcentration of analytes. However, SPME applies a short, thin rod of fused silica coated with the adsorbent, which is immersed in the liquid sample or in the closed headspace over the sample. After finishing the adsorption process, the analytes are thermally desorbed and analyzed by common chromatographic separation technique. A new ceramiccarbon composite was synthesized and its adsorption characteristics as SPME coating was investigated and compared with those of commercial preparations (PA, Car/ PDMS, PDMS/DVB and PDMS). It was found that the adsorption capacity of the new composite did not change in the tempera-

Porous graphitized carbon as stationary phase

Porous graphitized carbon (PGC) has been employed not only as an adsorbent and SPE and SPME coating, but also a stationary phase for the separation of a wide variety of solute molecules. Its application in HPLC has been recently reviewed. Its use in pharmaceutical, environmental and food analysis, and in biochemical and biophysical research and development, has been discussed in detail (Pereira, 2008). The concentration of 2-acetyl-4-(1,2,3,4-etrahydroxybutyl) imidazole (THI) in class III caramel colors was determined by heart-cutting two-dimensional liquid chromatography. The investigations were motivated by the immunotoxicity of THI. Samples were separated in the first dimension on an ODS or on a strong cationic exchanger stationary phase. The second dimension used a PGC column. It was found that the ODS-PGC column combination can be employed for the quantitative determination of THI in class III caramel colours (Moretton et al., 2008). The performance of PGC stationary phase for packed column supercritical fluid chromatography (SFC) was investigated and compared with those of another 27 stationary phases. A new classification system was developed to select the most suitable stationary phase for the solution of any separation problem (West and Lesellier, 2008). Similar results and considerations were published in a separate publication (Lesellier, 2008). An automated fractionation method was developed for the group separation of PCBs, PAHs, hydroxy-, keto- and nitro-PAHs,

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T. Cserhti sulfur, oxygen and nitrogen heterocycles. Cyanopropyl- and nitrophenylpropyl-bonded silica and PGC columns were coupled and automatically connected. It was established that the analytes are separated according to their polarity, the number of aromatic carbons and sterical characteristics. Because of the good group-specific separation capacity, high reproducibility and recoveries, the method was proposed for the fractionation of these environmental pollutants in sediments (Lbcke-von Varel et al., 2008. PGC stationary phase has also found application in the separation of famotidine and related impurities in pharmaceutical preparations. Mobile phase consisted of ACNwater (1:1, v/v) containing 0.5% pentane sulfonic acid. Inter- and intraday RSDs were less than 2%. Recovery was over 98%. The procedure was proposed for the determination of famotidine and impurities in commercial products (Helali and Monser, 2008). A narrow-bore PGC column was employed for the separation of betamethasone and dexamethasone in urine. The effect of analytical conditions was investigated in detail. The measurements indicated that the column temperature and the type of organic modifier exert a marked impact on the separation while the type of the organic acid was negligible (Oueslati et al., 2007). HPLC using a PGC column (100 2.1 mm; particle size, 3 m) was applied for the separation and quantitative determination of acrylamide in a wide variety of food and food products (potato crisps, pastry products, dried fruits, olives). The isocratic mobile phase consisted of methanolwater (5:95, v/v). The analyte was detected by tandem mass spectrometry. The RSD values were in each case below 12% (Bermudo et al., 2008). alkanes, aromatic compounds and chlorohydrocarbons were used as model compounds. It was found that both the capacity and strength of adsorption decrease after the oxidant treatment of carbon nanofibers (Cuervo et al., 2008). MWCTNs were modified with octadecyl amine and polyethylne glycol and the adsorption characteristics of the original and modified MWCTNs were compared. Pentachlorophenol, 2,4,5tricholorophenol, 3,3,4,4-tetrachlorobiphenyl, and 2,2,5,5tetrabromobiphenyl were used as model analytes. It was also found that the acetone was the best solvent for the desorption of analytes. It was suggested that the method can be applied for the simultaneous determination of environmental pollutant in water samples (Salam and Burk, 2008). The extraction capacity of MWCNTs, ODS and GCB was compared in the preconcentration of leachable pesticide residues (atrazine, dicloran, metazachlor and simazine). Pesticides were separated and quantitatively determined by HPLC. The results proved that MWCNTs has the highest adsorption capacity. The LOD values were 515 ng/L; the RSDs varied between 2.5 and 4.6%. Recoveries in tap water and well water were 92.795.3 and 85.387.0%, respectively (Al-Degs and Al-Ghouti, 2008). MWCNTs were successfully applied for the preconcentration of atrazine and its principal metabolites in water and soil samples using GC/MS. Atrazine, deisopropyl-atrazine (DIA) and deethylatrazine (DEA) were extracted from the samples by solvent methanolwater (1:1, v/v), cleaned up in SPE cartridges packed with MWCNTs using ethyl acetate for the elution of analytes. The LOD values for atrazine were 0.02 g/kg in water and 0.3 g/kg in soil. Recoveries were between 72.27 and 109.68%; the RSD was always lower than 13% (Min et al., 2008). The environmental pollutants fenpropathrin, cyhalothrin and deltamethrin were determined in water samples using MWCNT cartridges for preconcentration prior to HPLC analysis. The recoveries were between 91.7 and 117.8%. Because of the good validation parameters, the procedure was proposed for the separation and quantitative determination of this class of environmental pollutants (Zhou et al., 2008). An HPLC method was developed for the separation of the antidepressant trazodone and fluoxetine. Analytes were preconcentrated in cartridges containing MWCNTs and separated on a octylsilica column, the mobile phase containing the ionic liquid 1-butyl-3-methylimidazolium triflouoromethanesulfonate. The LOD values were 12.3 and 90.1 ng/mL for trazodone and fluoxetine, respectively, the RSD values being 3.45.0%. The method was proposed for the determination of these antidepressants in urine samples (Cruz-Vera et al., 2008). Carbon nanotubes have also been used as SPME fiber coating. The fiber showed good adsorption properties for benzene, toluene, ethylbenzene and o-xylene as verified by GC-FID. LOD values were between 0.09 and 0.39 /L and the repeatability was 5.913.3%. It was found that the procedure can be applied for the measurement of aromatic hydrocarbons in petrol station waste waters (Adomaviciute et al., 2008). The extraction efficacy of MWCNTs, cigarette filters and ODS was compared using di-butylphthalate and di-2-ethylhexylphthalate as model compounds. The separation and quantitative determination of the analyte were performed by HPLC. The measurements indicated that cigarette filters were the best adsorption agent. The recoveries were between 93.6 and 98.7%; RSDs varied between 1.40 and 1.72%; LOD was 3.1 ng/L. It was established that the method is suitable for the measurement of these environmental pollutants in drinking water (He et al., 2008).

Carbon Nanotubes
The relationship between nanotechnology and analytical chemistry, the application of nanodevices in analytical sciences and separation processes has been discussed in detail in excellent reviews (Valcrcel et al., 2008a,b). Various carbon nanotubes such as single-wall (SWNTs) and multi-wall nanotubes (MWNTs), as well as their carboxylic derivatives, have been extensively used as pseudostationary phases in electrokinetic chromatography (EKC). Their application can enhance the separation capacity of the system and/or can modify the retention order of analytes. The effect of SWNTs, MWNTs and C60 fullerenes on the EKC retention behavior of phenol, triazine and nitroimidazole derivatives was investigated in detail. It was established that the surfactant-coated CNs pseudostationary phases modified the retention behavior of analytes, improving separation (MolinerMartinez et al., 2008). The advantageous adsorption/desorption characteristics of carbon nanotubes have also been exploited for the fabrication of microtraps for large semivolatile organic molecules. The measurements indicated that the performance of SWNTs and MWCNTs were comparable and both showed better adsorption parameters than the commercially product CarbopackTM (Hussain et al., 2008a). The microtrapping characteristics of SWCNTs and MWCNTs were studied in detail and compared with those of CarbopackTM. Five different organic compounds served as analytes; their adsorption and desorption was followed by GCFID. Measurements suggested that both CNTs can be applied in microtraps (Hussain et al., 2008b). The influence of the functionalization of carbon nanofibers on the adsorption characteristics of VOCs has also been studied in detail employing inverse gas chromatography. Linear and cyclic

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Carbon-based sorbents in chromatography A new multi-layer adsorbent (Tenax TA/MWCNTs/Carboxeb 564) was developed and its extraction efficacy was compared with those of 11 commercial adsorbents. GC measurements indicated that the new adsorbent can be successfully applied for the determination of VOCs in indoor air (Liu et al., 2008). The in-situ synthesis of carbon nanotubes as new nanostructured stationary phases has also been reported, and the impact of the nanostructure on the retention of uracil, phenol, N,N-diethyl-m-toluamide and toluene was established (Fonverne et al., 2008). The extraction efficacy of MWCTNs, ODS and activated carbon (AC) was compared for the preconcentration of the herbicides propoxur, atrazine and methodathion. Extracts were analyzed by HPLC. It was established that the adsorption efficacy of MWCNTs was the highest but the performance of AC can be improved by adequate activation processes (El-Seikh et al., 2008). MWCNTs have also been employed as adsorbent of SPE for the analysis of PAHs in environmental waters. After the SPE step PAHs were separated and quantitatively determined by reversedphase HPLC using an ODS column (250 4.6 mm; particle size, 5 m). LOD values were 0.0050.058 /L; the recoveries and RSD values were 78.7118.1 and 1.74.8%, respectively. The new method was proposed for the determination of PAHs in water (Wang et al., 2007c). The preconcentration of diazinon, an organophosphorous insecticide, was also achieved using MWCTNs as the adsorbent. A glass SPE cartridge (50 10 mm i.d.) was packed with 50 mg of MWCNTs. The pH of the samples was adjusted to 6 by HCl or NaOH and 200 mL of the sample solution was passed through the cartridge. The bonded diazinon was eluted by 5 mL of ACN. HPLC measurements were performed by HPLC using an ODS column (150 4.5 m i.d. The mobile phase was ACNwater (65:35, v/v) at a flow rate of 1 mL/min. It was established that under optimal conditions the recovery of diazinon was 95.2 4.2%, the RSD being 4.9%. The LOD was 0.06 ng/mL. It was stated that the procedure can be applied for the accurate determination of diazinon in tap water (Katsumata et al., 2008). An interesting application of SWNTs in biochemical research was reported. Arginineglycineaspartic acidserine functionalized SWTNs has been successfully applied for the separation of bioactive molecules in affinity chromatography (Cheng et al., 2008). of traditional glassy carbon electrode. Kaempferol, retinol, retinyl acetate, cholecalciferol, -tocopherol and -tocopherol were included in the experiments. Analytes were separated on an ODS column (100 2.1 mm; particle size, 3 m). Isocratic measurements were performed by the mobile phase methanol5 mM sodium acetate buffer pH 3.8 (94:6, v/v). Gradient elution was carried out by eluent A (methanol water94:6, v/v), 5 mM sodium acetate buffer pH 3.8 and eluent B (methanol). The gradient started at 80% A (01.3 min), 1.4 19 min 100% A, 19.125 min 80% A. The working electrode potential was +1.30 V. It was established that the sensitivity of the new electrodes is higher than that of commercial glassy carbon electrodes (Chen and Jandik, 2008). A special silver-based solid carbon paste electrode was developed for the detection of iodide in ion-chromatography (IC). Separations were performed on an anion exchange column. Isocratic mobile phase consisted of methanolwater (50:50, v/v). Solid carbon paste was prepared by mixing micronized silver (23.5 m) or colloidal silver (<150 nm) with graphite and the hydrophobic binding agent (solid paraffin). Iodide in skim milk powder was determined by precipitating proteins from the reconstituted milk powder and the samples cleaned up on a carbonbased SPE column. The RSD value of the method was below 3%; the LOD value was 0.47 g/L. The application of the method for the measurement of iodide in table salts, sea products and iodide-bound drug compounds was proposed (Malongo et al., 2008). The concentration of catechin, rutin, kaempferol, gentistic acid and quercetin in Folium eriobotryae was measured using MAE or hot solvent extraction followed by capillary electrophoresis (CE). Solid samples were suspended in methanol and eposed to 700 W irradiation for 3 min. CE separation was carried out in a fused silica capillary of 40 cm length, and 25 m i.d. The running buffer was 50 mM borate buffer (pH 9.0). The capillary was thermostated at 25C. A three-electrode electrochemical cell consisting of a 300 m-diameter carbon disk detection electrode, aplatinum auxiliary electrode and a saturated calomel electrode as reference electrode was applied for the measurement of the analytes. The separation voltage was 12 kV, the electrode detection potential was +0.90 V. The RSD of the signals varied between 2.7 and 3.9%, while the RSD of the migration times was 1.22.6%. The detection limits were always below 4.5 M. It was stated that the method is suitable for the study of the constituents of plant drugs (Chen et al., 2008). A similar CE method was developed and applied for the measurement of rutin, gallic acid, quercetin and chlorogenic acid in green tea. The optimal electrophoretic conditions were: separation voltage, 18 kV, running buffer 60 mmol/L borate buffer (pH 8.7). Analytes were detected by a carbon disk electrode at 950 mV (vs saturated calomel electrode). The RSD values both for migration time and peak current were below 3%. The method was proposed for the determination of analytes in green tea (Li et al., 2008). A new HPLC method using amperometric detection was developed and applied for the measurement of thymol in various pharmaceutical preparation. The LOD value at the optimal conditions (+1.1 V vs AgAgCl/3 mol/L KCl in the mobile phase consisting of diluted BrittonRobinson buffer pH 7methanol, 1:9, v/v) was 2.9 107 mol/L The RSD values for the peak areas and peak height were 2 and 5%, respectively (Zima et al., 2007). MWCNT-based electrodes were also applied in micellar electrokinetic chromatography. Electrodes were prepared either by immobilizing a layer of MWCNTs dispersed in polyethyleneimine (PEI) or ethanol onto glassy carbon electrodes or prepared from

Carbon electrodes
Various carbon preparations have also been employed as electrodes for the sensitive detection of analytes after the chromatographic separation process. The electrochemical methods of detection are inexpensive, have low detectiom limits and are reliable and reproducible. An HPLC method was developed for the separation and quantitative determination of the synthetic dyes sudan I, sudan II, sudan III and sudan IV in food. Analytes were separated on an ODS column usin ACN20 mM acetate buffer (90:10, v/v) as mobile phase. Glassy carbon electrode and an MWTNionic liquid gel-modified glassy carbon electrode were employed for the detection of dyes. The detection limit of the method varied between 0.001 and 0.005 ppm. Because of the high sensitivity and selectivity of the procedure, it was proposed for the determination of this class of dyes in soft drink samples (Chailapakul et al., 2008). Thin-film carbon electrodes were prepared by physical vapor deposition of the electrode material on a polyetherketone support. The performance of the new electrodes was compared with that

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T. Cserhti paste electrodes employing mineral oil as a binder. Measurements indicated that the mode of preparation of electrodes exerts a considerable influence for the electrocatalytic activity, background current and electroanalytical characteristics. It was found that the best results were achieved by applying glassy carbon electrodes modified with MWCNTs. The suitability of the method was proven for the separation of phenolic environmental pollutants (phenol, 3-chlorophenol, 2,3-dichlorophenol and 4-nitrophenol) and herbicides such as amitrol, asulam, diuron, fenuron, monuron and chlortoluron (Chicharro et al., 2007).
Bermudo E, Moyano E, Puignou L and Galceran MT. Liquid chromatography coupled to tandem mass spectrometry for the analysis of acrylamide in typical Spanish products. Talanta 2008; 76: 389394. Blanco F, Vilanova X, Fierro V, Celzard A, Ivanov P, Llobet E, Canellas N, Ramirez JL and Correig X. Fabrication and characterisation of microporous activated carbon-based pre-concentrators for benzene vapours. Sensors and Actuators B: Chemical 2008; 132: 9098. Braida I, Mattea M and Cardarelli D. Extraction-adsorption-desorption process under supercritical condition as a method to concentrate antioxidants from natural sources. The Journal of Supercitical Fluids 2007; 45: 195199. Castells P, Parera J, Santos FJ and ans Galceran MT. Occurrence of polychlorinated naphthalenes, polychlorinated biphenyls and shortchain chlorinated paraffins in marine sediments from Barcelona (Spain). Chemosphere 2008; 70: 15521562. Chai X, Jia J, Sun T and Wang Y. Suitability of a novel circulating cooling SPME for the analysis of organophosphorous pesticides in tomatoes. Chromatographia 2008; 67: 309313. Chailapakul O, Wonsawat W, Siangproh W, Grudpan K, Zhao Y and Zhu Z. Analysis of sudan I, sudan II, sudan III and sudan IV in food by HPLC with electrochemical detection: comparison of glassy carbon electrode with carbon nanotubeionic liquid gel modified electrode. Food Chemistry 2008; 109: 876882. Chen Z, Zhang L and Chen G. Microwave-assisted extraction followed by capillary electrophoresisamperometric detection for the determination of antioxidant constituents in Folium eriobotryae. Journal of chromatography A 2008; 1193: 178181. Cheng J and Jandik P. New type of microfabricated carbon electrodes for high performance liquid chromatographyamperometric detection of fat-soluble vitamins and antioxidants. Journal of Chromatography A 2008; 11981199: 148153. Cheng W, Ding L, Lei JP, Ding SJ and Ju HX. Effective cell capture with tetrapeptide-functionalized carbon nanotubes and dual signal amplification for cytosensing and evaluation of cell surface carbohydrate. Analytical Chemistry 2008; 80: 38673872. Chicharro M, Arribas AS, Moreno M, Bermejo I and Zapardiel A. Comparative study of multi walled carbon nanotubes-based electrodes in micellar media and their application to micellar electrokinetic chromatography. Talanta 2007; 74: 376386. Cruz-Vera M, Lucena R, Crdenas S and Valcrcel M. Combined use of carbon nanotubes and ionic liquid to improve the determination of antidepressant in urine samples by liquid chromatography. Analytical and Bioanalytical Chemistry 2008; 391: 11391145. Cuervo MR, Asedegbega-Nieto, Diaz E, Vega A, Ordonez S, CastillejosLpez E and Rodriguez-Ramos I. Effect of carbon nanofiber functionalization on the adsorption properties of volatile organic compounds. Journal of Chromatography A 2008; 1188: 264 273. El-Seikh AH, Insisi AA and Sweileh JA. Effect of oxidation and dimensions of multi-walled carbon nanotubes on solid phase extraction and enrichment of some pesticides from environmental waters prior to their simultaneous determination by high performance liquid chromatography. Journal of Chromatography A 2007; 1164: 2532. El-Seikh AH, Sweileh JA, Al-Degs YS, InsisiAA and Al-Rabady N. Critical evaluation and comparison of enrichment efficiency of multi-walled carbon nanotubes, C18 silica and activated carbon towards some pesticides from environmental waters. Talanta; 2008; 74: 16751680. Fonverne A, Ricoul F, Demesmay C, Delattre C, Fournier A, Dijon J and Vinet F. In situ synthesized carbon nanotubes as a new nanostructured stationary phase for microfabricated liquid chromatographic colum. Sensors and Acuators B: Chemical 2008; 129: 510517. Gur-Reznik S, Katz I and Dosoretz CG. Removal of dissolved organic matter by granular-activated carbon adsorption as a pretreatment to reverse osmosis of membrane bioreactor effluents. Water Research 2008; 42: 15951605. He Y and Liu YH. Assessment of primary and secondary amine adsorbents and elution solvents with or without graphitized carbon for the SPE cleanup of food extracts in pesticide residue analysis. Chromatographia 2007; 65: 581590. He J-X, Fang G-Z, Jiand L-Q, Zhu H-P and Wang S. Evaluation of solid sorbents for the determination of di-butylphthalate and di-2ethylhexylphthalate in drinking water. International Journal of Environmental Analytical Chemistry 2008; 88: 317326. Helali N and Monser L. Stability indicating method for famotidine in pharmaceuticals using porous graphitic carbon column. Journal of Separation Science 2008; 31: 276282.

Miscellaneous Applications
Because of the widespread application of a high variety of carbon preparations in different chromatographic techniques, the physicochemical parameters of carbons such as adsorption strength, selectivity of adsorption, adsorption capacity and surface characteristics influencing retention were also investigated by chromatographic methods. Thus, inverse gas chromatography (IGC) was applied for the investigation of the surface characteristics of graphites milled during 1, 2, 3 and 4 h. IGC investigations were performed in both infinite dilution conditions (ID-IGC) and finite concentration (FC-IGC) conditions. The measurements allowed the determination of the surface homogeneity, the dispersive component of the surface energy, the nanomolecular and irreversibility indices, the isotherm of desorption, and the lateral energies of interaction. ICD was performed on stainless steel columns using an FID detection system. It was concluded from the measurements that IGC is an adequate method for the determination of the physicochemical surface properties of graphite samples Furthermore, the investigations proved that the milling increases the formation of high-energy sites and increases the nano-roughness of the surface (Balard et al., 2008). Another GC technology was applied for the study of the surface properties of nanodiamonds using n-hydrocarbons, benzene and other polar compounds. The surface of nanodiamonds was treated by boiling sulfochromic acid or by gaseous ozone. Marked differences in the retention characteristics of the samples was observed (Belyakova et al., 2008). Not only IGC but also inverse liquid chromatography (ILC) was employed for the study of the adsorption characteristics of carbon used for rubber application. It was established that ILC measurements are suitable for the determination of the heterogeneity of the surface of carbon black and the distribution of adsorption energy (Maafa et al., 2007).

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