Background: The biological activity and pharmacological effects of rare ginsenosides have been proven to be superior to those of the major ginsenosides, but they are rarely found in ginseng. Methods: Ginsenoside Rb1 was chemically transformed with the involvement of methanol molecules by a synthesized heterogeneous catalyst 12-HPW@MeSi, which was obtained by the immobilization of 12-phosphotungstic acid on a mesoporous silica framework. High-performance liquid chromatography coupled with mass spectrometry was used to identify the transformation products. Results: A total of 18 transformation products were obtained and identified. Methanol was found to be involved in the formation of 8 products formed by the addition of methanol molecules to the C-24 (25), C-20 (21) or C-20 (22) double bonds of the aglycone. The transformation pathways of ginsenoside Rb1 involved deglycosylation, addition, elimination, cycloaddition, and epimerization reactions. These pathways could be elucidated in terms of the stability of the generated carbenium ion. In addition, 12-HPW@MeSi was able to maintain a 60.5% conversion rate of Rb1 after 5 cycles. Conclusion: Tandem and high-resolution mass spectrometry analysis allowed rapid and accurate identification of the transformation products through the characteristic fragment ions and neutral loss. Rare ginsenosides with methoxyl groups grafted at the C-25 and C-20 positions were obtained for the first time by chemical transformation using the composite catalyst 12-HPW@MeSi, which also enabled cyclic heterogeneous transformation and facile centrifugal separation of ginsenosides. This work provides an efficient and recyclable strategy for the preparation of rare ginsenosides with the involvement of organic molecules.
Park, Jung-Eun;Park, Jae-Hyun;Yim, Sung-Dae;Kim, Chang-Soo;Park, Eun-Duck
Korean Chemical Engineering Research
/
v.49
no.1
/
pp.21-27
/
2011
The comparison work was conducted for the methanol steam reforming among commercial Cu-based catalysts, viz. ICI-M45, which is for the methanol synthesis, MDC-3 and MDC-7, which are for the water-gas shift reaction. The catalytic activity for the water-gas shift reaction was also compared over three catalysts. Among them, MDC-7 showed the highest methanol conversion and formation rate of hydrogen and carbon dioxide at 473 K for the methanol steam reforming. To find out any promotional effect between ICI-M45 and MDC-7, three different packing methods with these two catalysts were examined. However, no synergistic effect was observed. The catalytic activity for watergas shift reaction decreased in the following order: MDC-7 > MDC-3 > ICI-M45. The highest activity of MDC-7 for the methanol steam reforming as well as the water-gas shift reaction can be due to its high surface area, copper dispersion, and an adequate Cu/Zn ratio.
The effect of water activity on degradation of pigments in dried lavers, Porphyra tenera Kjellm. was examined when stored at room temperature for fifty days. Chlorophyll pigment was extracted with methanol-petroleum ether mixture solvent(2:1 v/v), partitioned in ether, and analysed spectrophotometrically at 662 nm as chlorophyll a. The degradation products of chlorophyll were isolated on sugar-starch column(85:15 w/w) with n-propanol-petroleum ether solution(1:200 v/v) as a developing solvent. The isolated green colored zones were analysed individually at the wavelengths of 650, 662, and 667 nm as allomerized product, chlorophyll a retained, and pheophytin formed respectively. Carotenoida were also extracted with the methanol mixture solvent, partitioned in ether, and finally redissolved in acetone after the evaporation of ether in a rotary vacuum evaporator. The total carotenoid content was measured as lutein at 450 nm. From the results, it is noted that the rate of chlorophyll degradation reached a minimum at 0.11 to 0.33 water activity while progressively increased at higher moisture levels resulting in rapid conversion of chlorophyll to pheophytin. At lower activity, autocatalysed oxidizing reaction like allomerization seemed prevailing the acid catalysed conversion reaction. The loss of carotenoid pigment was also greatly reduced at the range of 0.22 to 0.34 water activity with much faster oxidative degradation at both higher and extremely lower moisture levels. These two moisture levels indicated above at which the both pigments exhibited maximum stability are considerably higher than the BET monolayer moisture which appeared 7.91 percent on dry basis at Aw=0.10 calculated from the adsorption isothermal data of the sample at $20^{\circ}C$. The rate of pigment loss in heat treated samples at 60 and $100^{\circ}C$ for 2 hours prior to storage somewhat decreased, particularly at higher moisture levels although the final pigment retention was not much stabilized.
Bang, Byoung Man;Park, No-Kuk;Han, Gi Bo;Yoon, Suk Hoon;Lee, Tae Jin
Korean Chemical Engineering Research
/
v.45
no.6
/
pp.566-572
/
2007
Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.
Journal of the Korean Applied Science and Technology
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v.36
no.1
/
pp.355-361
/
2019
The red pigment extracted from Serratia marcescens 2354 (ATCC 25419) was prodigiosin (PG), which was dissolved in methanol and measured for ultraviolet and visible light absorption spectra. It was the typical absorption spectrum of PG in an acid solution with ${\lambda}_{max}=537nm$. When the concentration of PG was increased from $1.0{\times}10-5M$ to $9.0{\times}10-5M$ in the methanol solution, the absorption intensity at 537 nm was increased, the absorption intensity at 467 nm was decreased, and the isosbestic point at 500 nm was observed. This phenomenon can be regarded as a result of reversible acid-base equilibrium reaction considering 537 nm and 467 nm of PG absorption band in acid and base solution respectively and isosbestic point of 500 nm. On the other hand, when the concentration of PG was reduced from $6.0{\times}10-4$ to $1.0{\times}10-4M$ in acetic acid buffer solution at pH 4.75, a new absorption band with ${\lambda}$ max at 500 nm appeared. This absorption band appears only in the aqueous solution of pH 4.75 and does not appear in the pure methanol solution of the same pH. This is due to the conversion of the PG molecule from the ${\alpha}$-isomer to the ${\beta}$-isomer by $H_2O$. In other words, it was confirmed that the color change of the PG can be caused by the concentration of the solution and the characteristics of the solvent.
Transactions of the Korean Society of Mechanical Engineers B
/
v.27
no.11
/
pp.1563-1571
/
2003
This paper is the second part of several companion papers which compare the method of Air-fuel ratio(AFR) determination. In the previous paper, Eltinge chart was applied to the arbitrary fuel composition and the charts for gasoline, diesel, methanol, M85, liquefied petroleum gas(LPG), natural gas(NG), propane and butane were illustrated. In Eltinge chart, however, unburned hydrocarbon (UHC) is not used for determination of AFR. For improving accuracy, Eltinge suggested UHC compensation after the AFR reading in the chart. This compensation reduced the difference between real and reading value. In the compensation, however, the correction of oxygen and carbon dioxide is uncertain and there might be a mistake in conversion of UHC reading value. Therefore, the error is overestimated comparing with Spindt one which is most widely used. In addition, there is no comparison of the value with other useful methods. In this paper, the compensation of unburned HC was performed in Eltinge chart and the compensated value was compared with Spindts formula over wide range of AFR. The objects of investigating fuel are gasoline, methanol, NG and LPG. The result shows that Eltinge and Spindt method is flawlessly compatible and the difference between the two methods is under 0.3% in a λrange from 0.9 to 1.7. The method fur debugging instrumentation error is also presented.
Wang Hak-Min;Choi Kap-Seung;Kang Il-Hwan;Kim Hyung-Man;Erickson Paul A.
Journal of Mechanical Science and Technology
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v.20
no.6
/
pp.864-873
/
2006
As fuel cells approach commercialization, hydrogen production becomes a critical step in the overall energy conversion pathway. Reforming is a process that produces a hydrogen-rich gas from hydrocarbon fuels. Hydrogen production via autothermal reforming (ATR) is particularly attractive for applications that demand a quick start-up and response time in a compact size. However, further research is required to optimize the performance of autothermal reformers and accurate models of reactor performance must be developed and validated. The design includes the requirement of accommodating a wide range of experimental set ups. Factors considered in the design of the reformer are capability to use multiple fuels, ability to vary stoichiometry, precise temperature and pressure control, implementation of enhancement methods, capability to implement variable catalyst positions and catalyst arrangement, ability to monitor and change reactant mixing, and proper implementation of data acquisition. A model of the system was first developed in order to calculate flowrates, heating, space velocity, and other important parameters needed to select the hardware that comprises the reformer. Predicted performance will be compared to actual data once the reformer construction is completed. This comparison will quantify the accuracy of the model and should point to areas where further model development is required. The end result will be a research tool that allows engineers to optimize hydrogen production via autothermal reformation.
Kim, Dong-Woo;Park, Moon-Seok;Kim, Moon-Il;Park, Dae-Won
Korean Chemical Engineering Research
/
v.50
no.2
/
pp.217-222
/
2012
The synthesis of dimethyl carbonate(DMC) is a promising reaction for the use of naturally abundant carbon dioxide. DMC has gained considerable interest owing to its versatile chemical reactivity and unique properties such as high oxygen content, low toxicity, and excellent biodegradability. In this study, the synthesis of DMC through the transesterification of ethylene carbonate(EC) with methanol was investigated by using ionic liquid and metal oxide catalysts. The screening test of different catalysts revealed that choline hydroxide ([Choline][OH]) and 1-n-butyl-3-methyl imidazolium hydroxide([BMIm][OH]) had better catalytic performance than metal salts catalysts such as MgO, ZnO and CaO. The effects of reaction parameters such as reaction temperature, MeOH/EC mole ratio, and carbon dioxide pressure on the reactivity of [Choline][OH] catalyst were discussed. High temperature and high MeOH/EC mole ratio were favorable for high conversion of EC. However, the yield of DMC showed a maximum when carbon dioxide pressure was 1.34 MPa, and then it decreased for higher carbon dioxide pressure. Zinc chloride($ZnCl_2$) was used as co-catalyst with the ionic liquid catalyst. The mixed catalyst showed a synergy effect on the EC conversion and DMC yield probably due to the acid-base properties of the catalysts.
The influence of acidity in MTT zeolite of different Si/Al molar ratio's on the catalyst activity in methanol-to-olefin (MTO) reaction has been investigated. The Si/Al ratio was controlled with the Al content in the gel when N,N,N',N'-tetramethyl-1,3-diaminopropane was used as a structure directing agent (SDA). The gel composition was controlled to $20SiO_2$ : 30SDA : x (=0.25~1.25)$NaAlO_2$ : 2NaOH : $624H_2O$, which was subject to the hydrothermal synthesis at 433 K for 4 days. As the composition of sodium aluminate decreased, the particle size of MTT zeolite increased, and also the amount of acid sites decreased. To investigate the catalytic performance, MTO reaction was carried out at 673 K with $1.2h^{-1}$ WHSV. It was found that the H-MTT (1.00Al) catalyst with a Si/Al molar ratio of 24 maintained the methanol conversion over 90% for 900 min.
Kim, Bo-Kyung;Koh, Jae-Cheon;Kim, Beom-Sik;Han, Myung-Wan
Korean Chemical Engineering Research
/
v.49
no.2
/
pp.155-160
/
2011
Dimethyl ether draws an attention as a green fuel in recent years. In this study, we investigated dehydration of methanol to produce DME using solid-acid catalysts, a series of zeolite. We found that ceria took a role of promoting the reaction conversion as well as selectivity of DME formation as a cocatalyst to the zeolite catalyst. We varied Si/Al ratio and ceria percentage on the surface of the catalyst to get high performance catalyst. ZSM5-30 with 5 wt% ceria on the surface was found to have excellent DME selectivity and to be little influenced by water content in methanol feed. We proposed a reaction model and obtained kinetic parameters for the DME formation using the catalyst based on experimental results using a microreactor.
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