基于石墨化炭黑预涂覆技术的色谱柱制备和性能评价

采用石墨化炭黑(GCB)预涂覆技术对白酒分析专用色谱柱(LZP-930)的制备方法进行了优化,详细考察了所制备的色谱柱(LZP-930G)的性能参数,并对LZP-930G色谱柱的保留行为进行了评价,探讨了GCB对LZP-930G色谱柱性能的影响。研究发现,LZP-930G色谱柱的柱效、惰性、稳定性和极性均得到了明显提高,从而改善了酸类和醇类组分的分离选择性和色谱峰峰形,实现了白酒中53种易挥发和半挥发性微量组分的同时分离,且各组分的保留时间和峰面积的相对标准偏差分别小于0.63%和4.51%(n=5)。表明GCB预涂覆技术能够用于高性能白酒分析色谱柱的制备方法。     

Adsorption of cyclic amines on graphitized thermal carbon black

Thermodynamic characteristics of adsorption (TCA) for aniline and its methyl derivatives on the surface of graphitized thermal carbon black (GTC, Carbopack C HT trade mark) were determined using equilibrium gas adsorption chromatography in the range of the lowest adsorbate concentrations in the gas phase. A series of relationships relating the TCA of the studied amines to their physicochemical parameters was obtained. The theoretical values of entropy of adsorption were calculated in the framework of the model of two-dimensional ideal gas and compared with the corresponding experimental values, which allowed one to reveal specific features of the molecular structure of the adsorbates. A similarity between the thermal component of entropy of the studied compounds in the adsorbed state and that of the entropy of the pure liquid adsorbates made it possible to refine the physical state and mobility of the adsorbate molecules in the force field of the adsorbent. The regression equation relating the heats of adsorption on the GTC to such molecular constants of adsorbates as polarizability, molecular surface area, and molecular weight were proposed for the first time. A high predictive power of the equations derived in the work for the preliminary estimation of the adsorption characteristics of alkylanilines and alkylbenzenes on the GTC was shown.     

Adsorption behavior of Vulkan-7H graphitized carbon black

The adsorption behavior of Vulkan-7H carbon black graphitized at 3073 K was studied. Benzene adsorption isotherms at 293 K were measured by the static method and by gas chromatography. It was shown that Vulkan-7H carbon black may be considered as a supermicroporous adsorbent with a pore size of 1.05 nm.The sample was provided by N. N. Lezhnev.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1544–1546, September, 1993.     

Adsorption of adamantanol isomers on graphitized thermal carbon black

The thermodynamic characteristics of adsorption of some adamantanol isomers on graphitized thermal carbon black were calculated and determined experimentally. The parameters of the potential function for the intermolecular interaction between hydroxyl oxygen and carbon of the graphite basis plane were determined for the first time. The adsorption properties of adamantanols are largely determined by electron density distribution in the adamantane cage, which are related to the cage effect.     

SALDI-MS Signal enhancement using oxidized graphitized carbon black nanoparticles

The signal intensity of low-molecular-weight compounds analyzed using surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF-MS) was significantly enhanced when oxidized graphitized carbon black (GCB) particles were used as the desorption/ionization surface. The surface of oxidized GCB contains more carboxylic acid groups than non-oxidized GCB. Carboxylic acid groups enhance the efficiency of the ionization process and the desorption of more hydrophobic compounds. A common pharmaceutical compound, propranolol, was successfully extracted from Baltic Sea blue mussels and quantified using oxidized GCB as the SALDI surface, whereas deuterated propranolol was used as the internal standard. The calibration curve showed a wide linear dynamic range of response (0.1–20 μg/mL) and good reproducibility (RSD < 10%). It was not possible to detect propranolol in Baltic Sea blue mussels when non-oxidized GCB was used as the SALDI surface.     

Solid-phase extraction of polar pesticides from environmental water samples on graphitized carbon and Empore-activated carbon disks and on-line coupling to octadecyl-bonded silica analytical columns

The suitability of Empore-activated carbon disks (EACD), Envi-Carb graphitized carbon black (GCB) and CPP-50 graphitized carbon for the trace enrichment of polar pesticides from water samples was studied by means of off-line and on-line solid-phase extraction (SPE). In the off-line procedure, 0.5-2 1 samples spiked with a test mixture of oxamyl, methomyl and aldicarb sulfoxide were enriched on EnviCarb SPE cartridges or 47 mm diameter EACD and eluted with dichloromethane-methanol. After evaporation, a sample was injected onto a C₁₈-bonded silica column and analysed by liquid chromatography with ultraviolet (LC-UV) detection. EACD performed better than EnviCarb cartridges in terms of breakthrough volumes (>2 1 for all test analytes), reproducibility (R.S.D. of recoveries, 4–8%, n=3) and smapling speed (100 ml/min); detection limits in drinking water were 0.05–0.16 μg/l. In the on-line experiments, 4.6 mm diameter pieces cut from original EACD and stacked onto each other in a 9 mm long precolumn, and EnviCarb and CPP-50 packed in 10×2.0 mm I.D. precolumn, were tested, and 50–200 ml spiked water samples were preconcentrated. Because of the peak broadening caused by the strong sorption of the analytes on carbon, the carbon-packed precolumns were eluted by a separate stream of 0.1 ml/min acetonitrile which was mixed with the gradient LC eluent in front of the C₁₈ analytical column. The final on-line procedure was also applied for the less polar propoxur, carbaryl and methiocarb. EnviCarb could not be used due to its poor pressure resistance. CPP-50 provided less peak broadening than EACD: peak widths were 0.1–0.3 min and R.S.D. of peak heights 4–14% (n = 3). In terms of analyte trapping efficiency on-line SPE-LC-UV with a CPP-50 precolumn also showed better performance than when Bondesil C₁₈/OH or polymeric PLRP-S was used, but chromatographic resolution was similar. With the CPP-50-based system, detection limits of the test compounds were 0.05–1 μg/l in surface water.     

Stability of organophosphorus insecticides on graphitized carbon black extraction cartridges used for large volumes of surface water

The stability of nine organophosphorus insecticides (azinphos-ethyl, azinphos-methyl, diazinon, EPN, ethion, fonofos, malathion, phosmet and parathion-methyl) was evaluated under a variety of storage conditions. Large volumes of surface water (4 l) were extracted using large-particle-size graphitized carbon black cartridges (Carbopack B 60-80 mesh). The effects of temperature, matrix type and drying of cartridges on the recovery of these contaminants, after different storage periods, were studied and compared to the conservation of surface water in bottles. After a 2-month period, all the chemicals stored on cartridges and kept at -20 degrees C remained stable, with recoveries ranging from 70 to 134%. By contrast, phosmet and EPN could no longer be recovered from the bottled surface water. Cartridges kept at -20 degrees C fared better than did those stored at 4 degrees C and 20 degrees C. The type of matrix water selected appears to have kept the target pesticides stored on cartridges from degrading, compared to the Milli-Q water, in which malathion and phosmet were unstable. The effect of the cartridges being either wet or dry made no difference in terms of improving the recovery of chemicals. After immediate surface water extraction, the most practical storage condition for the target insecticides was found to be storage on cartridges in the dark at -20 degrees C, with no drying or solvent washing of the Carbopack B material.     

Solid phase microextraction using fused silica fibers coated with graphitized carbon black

Summary This paper presents the results obtained using fused-silica fibers coated with graphitized carbon black (Carbograph-Alltech) for solid-phase microextraction (SPME). The extraction and calibration curves relative to organic micro-pollutants present in gaseous and aqueous samples are reported. Examples of applications of this extraction procedure to GC and GC-MS analysis of organic micro-pollutants in actual samples are also reported.     

The nature of surface chemical heterogeneities of graphitized carbon black

Experimental evidence is presented for the existence of quinone, aromatic ether, carboxylic acid and phenol groups on the surface of a graphitized carbon black (GCB), that is P-33 (2700°C). This evidence has been achieved by using polarographic analysis of a slurry of GCB particles.Polarographic analysis has been also performed for ungraphitized P-33.By comparison, it appears that the heating at 2700°C does not remarkably change the nature and the amount of chemical groups chemically bound to the surface of the carbon black.     

Retention of some phenyl-substituted and bicyclic hydrocarbons on graphitized carbon black

Summary Retention volume values for zero cample size (Henry's constants) at different temperatures, retention indices and differential adsorption heats of phenylethylene, phenylacetylene, C₉–C₁₂ phenylcyclanes, biphenylethylenes, biphenylacetylene, bicyclohexyl and bicyclohexylmethane have been determined on graphitized thermal carbon black (GTCB). The molecules of all these hydrocarbons are capable of internal rotation. The values of the thermodynamic adsorption characteristics of phenylcyclanes increase with increasing number of carbon atoms in the cycle. Bicyclohexyl is retained on GTCB considerably weaker than biphenyl while bicyclohexylmethane is retained stronger than biphenylmethane. Symmetric and nonsymmetric biphenylethylenes are retained much stronger than the corresponding biphenylethanes. Phenylethylene (styrene) and trans-biphenylethylene (trans-stilbene) are stronger retained on GTCB than phenylacetylene and biphenylacetylene (tolane), respectively. The relationship between the structure of these molecules and their retention on GTCB is discussed.     

Adsorption equilibria of binary gas mixtures on graphitized carbon black

Adsorption equilibria for binary gas mixtures (methane-carbon dioxide, methane-ethane, and carbon dioxide-ethane) on the graphitized carbon black STH-2 were measured by the open flow method at 293.2 K. The experimental pressure range was (0 to 1.6) MPa. The extended Langmuir (EL) model and the ideal adsorption solution theory (IAST) have been adopted to predict the equilibria of binary gas mixtures. The results indicate that gas mixtures adsorbed on the homogeneous surface of STH-2 exhibit the nonideal behavior, which is mainly induced by adsorbate-adsorbate interactions. The real adsorption solution theory (RAST) has been used to analyze the property of the adsorbed mixtures. The activity coefficients have been correlated with the Wilson equation. The investigation demonstrates that the nonideality of adsorbed phase is completely dissimilar with the bulk liquid phase. The adsorption of the heavier component would benefit the adsorption of the lighter component.     

The influence of an intramolecular H-bond on the adsorption of sulfur-containing amino acids on graphitized thermal carbon black

The thermodynamic characteristics of adsorption of sulfur-containing amino acids and their derivatives on the surface of graphitized thermal carbon black were calculated by the molecular statistical method. The parameters of the atom-atom potential function of intermolecular interaction between the S atom in amino acids and the graphite C atom were determined. It was shown that an intramolecular H-bond influenced the adsorption of amino acids on the surface of graphitized thermal carbon black.     

Gas chromatography-mass spectrometry in the study of the adsorption of sulfur-containing amino acids on graphitized thermal carbon black

Summary Gas chromatographic — mass spectrometric study of the trifluoroacetyl-methyl esters of sulfur- and hydroxyl-containing amino acids such as methionine, cysteine, D-,-dimethylcysteine (D-penicillamine), serine, and threonine was carried out. Sterling hydrogen treated graphitized thermal carbon black (HTGTCB) was used as the adsorbent. The Henry's constants, and the initial differential adsorption heats of these amino acid derivatives were determined on the HTGTCB surface by gas chromatography.Introduction of two methyl groups into the -position of a cysteine molecule (,-dimethylcysteine) stimulates the intramolecular nonvalent interactions increasing the internal rotation barriers in the molecule. This is revealed in the sharply reduced retention of the ,-dimethylcysteine derivative on the HTGTCB surface (as compared to the cysteine derivative) and it also influences the fragmentation pathways under electron impact.Deceased.     

Adsorption of benzyl alcohol and 1-phenylethanol on graphitized thermal carbon black

The adsorption of benzyl alcohol and 1-phenylethanol on graphitized thermal carbon black at 300 K is investigated. Thermodynamic characteristics of the adsorption of conformers stable in the gas phase and in the adsorbed state are determined by a molecular statistics method. The geometry of the molecules is optimized using the MP2 and B3LYP methods with a 6-311++G(d,p) basis set. Using the PBE0/6-31G(d) method, it is established that, in the adsorption of benzyl alcohol, two types of interactions, CH…O and OH…π_GTCB, occur. It is shown that, in 1-phenylethanol, intramolecular interactions are maintained.     

Gas chromatographic investigation of adsorption equilibria on graphitized thermal carbon black

Summary Retention volumes and heats of adsorption at low surface coverages of graphitized thermal carbon black (GTCB) for C₆–C₁₄ aromatic hydrocarbons have been determined. The dependence of heats of adsorption of these molecules on their structure and the number of carbon atoms in the molecule have been investigated. Substitution in the ring in methylbenzenes is not equivalent to the lengthening of the side-chain in the isomers of n-alkylbenzenes and gives rise to a much greater increase in the retention volumes and heats of adsorption.