• Bulletin of the Korean Chemical Society
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• v.30 no.8
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• pp.1755-1759
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• 2009

Surface structure and molecular orientation of self-assembled monolayers (SAMs) formed by the spontaneous adsorption of tetrahydrothiophene (THT) and thiophene (TP) on Au(111) were investigated by means of scanning tunneling microscopy (STM) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy. STM imaging revealed that THT SAMs have a commensurate (3 ${\times}\;2\sqrt[]{3}$) structure containing structural defects in ordered domains, whereas TP SAMs are composed of randomly adsorbed domains and paired molecular row domains that can be described as an incommensurate packing structure. The NEXAFS spectroscopy study showed that the average tilt angle of the aliphatic THT ring and $\pi$-conjugated TP ring in the SAMs were calculated to be about $30^o\;and\;40^o$, respectively, from the surface normal. It was also observed that the $\pi$* transition peak in the NEXAFS spectrum of the TP SAMs is very weak, suggesting that a strong interaction between $\pi$-electrons and the Au surface arises during the self-assembly of TP molecules. In this study, we have clearly demonstrated that the surface structure and adsorption orientation of organic SAMs on Au(111) are strongly influenced by whether the cyclic ring is saturated or unsaturated.

• Analytical Science and Technology
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• v.7 no.1
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• pp.79-89
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• 1994

Interactions between the acetonitrile and other organic molecules such as furan, pyrrole, pyrrolidine, thiophene, tetrahydrothiophene and acetaldehyde was studied with the infrared absorption spectroscopy under matrix isolation conditions. Xe was used as a major matrix material. Acetonitrile showed strong interactions with pyrrole and thiophene, and little interactions with pyrrolidine and acetaldehyde.

• Analytical Science and Technology
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• v.7 no.3
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• pp.349-359
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• 1994

A gas chromatographic method for analyzing the gas odorants concentration in natural gas was studied. Eight odorants involving TBM and THT were completely separated by using OV-10 column. The optimization of several interrelated key parameters affecting the response of FPD such as hydrogen flow rate, air flow rate and detector temperature were accomplished. A permeation device was used to obtain calibration curves of TBM and THT. This analytical method has applied to measure TBM and THT used as a natural gas odorant blend in natural gas pipeline. In order to elucidate the relationship between odor level and odorant level feasibility test of fragrance meter was demonstrated.

• Journal of Microbiology and Biotechnology
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• v.20 no.8
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• pp.1230-1239
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• 2010

Five bacterial species, capable of degrading the recalcitrant organic compounds (ROCs) diethyleneglycol monomethylether (DGMME), 1-amino-2-propanol (APOL), 1-methyl-2-pyrrolidinone (NMP), diethyleneglycol monoethylether (DGMEE), tetraethyleneglycol (TEG), and tetrahydrothiophene 1,1-dioxide (sulfolane), were isolated from an enrichment culture. Cupriavidus sp. catabolized $93.5{\pm}1.7$ mg/l of TEG, $99.3{\pm}1.2$ mg/l of DGMME, $96.1{\pm}1.6$ mg/l of APOL, and $99.5{\pm}0.5$ mg/l of NMP in 3 days. Acineobacter sp. catabolized 100 mg/l of DGMME, $99.9{\pm}0.1$ mg/l of NMP, and 100 mg/l of DGMEE in 3 days. Pseudomonas sp.3 catabolized $95.7{\pm}1.2$ mg/l of APOL and $99.8{\pm}0.3$ mg/l of NMP. Paracoccus sp. catabolized $98.3{\pm}0.6$ mg/l of DGMME and $98.3{\pm}1.0$ mg/l of DGMEE in 3 days. A maximum $43{\pm}2.0$ mg/l of sulfolane was catabolized by Paracoccus sp. in 3 days. When a mixed culture composed of the five bacterial species was applied to real wastewater containing DGMME, APOL, NMP, DGMEE, or TEG, 92~99% of each individual ROC was catabolized within 3 days. However, at least 9 days were required for the complete mineralization of sulfolane. Bacterial community diversity, analyzed on the basis of the TGGE pattern of 16S rDNA extracted from viable cells, was found to be significantly reduced in a conventional bioreactor after 6 days of incubation. However, biodiversity was maintained after 12 days of incubation in an electrochemical bioreactor. In conclusion, the electrochemical reduction reaction enhanced the diversity of the bacterial community and actively catabolized sulfolane.

• Korean Chemical Engineering Research
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• v.48 no.4
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• pp.534-539
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• 2010

The adsorptive removal of organic sulfur compounds including tert-butylmercaptane(TBM), tetrahydrothiophene(THT) and dimethylsulfide(DMS) in methane was investigated over NaY and copper-exchanged NaY(CuNaY) zeolites at 303 K and atmospheric pressure. In the ternary adsorption system, the preferential adsorption of THT over other sulfur compounds on NaY and the concurrent adsorption of all sulfur compounds on CuNaY were achieved, which could be explained by the breakthrough curve, the temperature-programmed desorption, and the apparent activation energy for desorption. The sulfur uptake capacity of CuNaY(2.90~3.20 mmol/g) was much higher than that of NaY(0.70~0.90 mmol/g). A comparative study indicated that the $Cu^{1+}$ sites and acidity of CuNaY were probably responsible for the strong interaction with sulfur atom and high sulfur uptake abilities.

• Journal of the Korean Chemical Society
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• v.42 no.6
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• pp.646-651
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• 1998

The molecular structure of sulfur compounds and the retention relationship are studied by gas chromatography. Analyzed sulfur compounds are, hydrogen sulfide, sulfur dioxide, carbon disulfide, ethyl mercaptan, dimethyl sulfide, iso-propyl mercaptan, normal propyl mercaptan, ethyl methyl sulfide, tert-butyl mercaptan, tetrahydrothiophene, thiophene, and 2-chlorothiophene. Multiple linear regression explains the retention relationship of molecular descriptors. In GC the temperature program is 30$^{\circ}C$ held for 10.5 min, and then increased to 150$^{\circ}C$ at a rate 15$^{\circ}C$/min. Predicted equation for relative retention time (RRT) using SAS program is as follows; $RRT=0.121bp+14.39dp-8.94dp^2+0.0741sqmw-35.78\; (N=8,\; R^2=0.989, \;Variance=0.175,\;F=66.21)$. RRTs are function of boiling point, the square root of molecular weight, molecular dipole moment, and boiling point effects mostly on RRT. The RRT is maximized at the molecular dipole moment of 0.805D, when using nonpolar columns. The planar and highly symmetric compounds are eluted slowly. The square, of correlation coefficient $(R^2)$ using SAS program, is 0.989, and the variance is 0.175 in training sets. For three sulfur compounds, the variance between observed RRTs and predicted RRTs is 0.432 in testing sets.

• Clean Technology
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• v.13 no.1 s.36
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• pp.64-71
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• 2007

The selection of a suitable adsorbent for removing organic sulfur compounds tetrahydrothiophene (THT) and t-butylmercaptan (TBM) from natural gas has been carried out. The saturation adsorption capacity for the sulfur compounds were determined by pulse adsorption method for a group of nanoporous materials, including Na-Y, Na-ZSM-5, Na,K-ET(A)S-10, Na-Mordenite, Na,K-Clinoptitolite, Ti/MCM-41, Ti/SBA-15 and amorphous titanosilicates. Among the materials tested, Na-Y and Na,K-ET(A)S-10 zeolites showed high adsorptive capacities for THT and TBM. The saturation capacity for THT on Na,K-ETS-10 was comparable with that on Na-Y zeolite, which is well known as an effective adsorbent. The capacity and adsorptivity for THT and TBM on Na,K-ETAS-10 were improved by an increase in crystallinity of Na,K-ETAS-10. An investigation of the competitive adsorption between THT and TBM from the breakthrough test using a simulated natural gas indicates that Na,K-ETS-10 selectively adsorbs THT. The breakthrough capacity for THT on Na,K-ETS-10 was 1.19 mmol/g. The results show that the high adsorption performance of Na.K-ETS-10 and Na,K-ETAS-10 is due to the highly exchanged cations in the zeolitic structure which exhibit the strong electrostatic interactions with organic sulfur compounds and their wide pore nature.

• Clean Technology
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• v.15 no.1
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• pp.60-66
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• 2009

Adsorptive removal of tetrahydrothiophene (THT) and tert-butylmercaptan (TBM) that were widely used sulfur odorants in pipeline natural gas was studied using various ion-exchanged NaY zeolites at ambient temperature and atmospheric pressure. In order to improve the adsorption ability, ion exchange was performed on NaY zeolites with alkali metal cations of $Li^+,\;Na^+,\;K^+$ and transition metal cations of $Cu^{2+},\;Ni^{2+},\;Co^{2+},\;Ag^+$. Among the adsorbents tested, Cu-NaY and Ag-NaY showed good adsorption capacities for THT and TBM. These good behaviors of removal of sulfur compound for Cu-NaY and Ag-NaY zeolites probably was influenced by their acidity. The adsorption capacity for THT and TBM on the best adsorbent Cu-NaY-0.5, which was ion exchanged with 0.5 M copper nitrate solution, was 1.85 and 0.78 mmol-S/g at breakthrough, respectively. It was the best sulfur capacity so far in removing organic sulfur compounds from fuel gas by adsorption on zeolites. While the desorption activation energy of TBM on the Cu-NaY-0.5 was higher than NaY zeolite, the difference of THT desorption activation energy between two zeolites was comparatively small.