• Bulletin of the Korean Chemical Society
• /
• v.33 no.7
• /
• pp.2295-2298
• /
• 2012

We describe herein a three-dimensionally diverse micropatterning of poly(lactic acid), as a biopolymer, using 1-butyl-3-methylimidazolium-based room-temperature ionic liquids (bmim-based RTILs), [bmim]X (X = $SbF_6$, $PF_6$, $NTf_2$, Cl). Utilizing the hydrophobic bmim-based RTILs, [bmim]X (X = $SbF_6$, $PF_6$, $NTf_2$) and a phase separation technique, we were able to produce white and opaque membranes with a three-dimensional structure closely packed with particles ($10-50{\mu}m$ in diameter). The particlulate structure, made by the assistance of [bmim]$NTf_2$ and DCM, interestingly transformed to a fibrous structure by using a cosolvent, e.g., DCM/$CF_3CH_2OH$. When we used an increased amount of [bmim]$NTf_2$, the particles were effectively detached and macrosized ($100-500{\mu}m$ in diameter) and the oval-shaped beads were obtained in a powder form. By varying the counter-anion type of the imidazolium-based RTIL, for example from $NTf_2^-$ to $Cl^-$, the particulate 3D-morphology was once more transformed to a porous structure. These reserch results could be potentially useful, as a method to fabricate particulate scaffolds, fibrous or porous scaffolds, and beads as a biopolymer device in diverse fields including drug delivery, tissue regeneration, and biomedical engineering.

• Korean Chemical Engineering Research
• /
• v.48 no.5
• /
• pp.583-588
• /
• 2010

Esterification of free fatty acid with methanol to biodiesel was investigated in a batch reactor using various solid acid catalysts, such as polymer cation-exchanged resins with sulfuric acid functional group(Amberlyst-15, Dowex 50Wx8), acidic ionic liquids (ILs)-modified silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-[ASBI][HSO_4]$, $SiO_2-[ASCBI][HSO_4]$) and grafted silica gels respectively with $-SO_3H$ and $-SO_2Cl$ functional group ($SiO_2-R-SO_3H$, $SiO_2-R-SO_2Cl$). The effects of reaction time, temperature, reactant concentration(molar ratio of methanol to oleic acid), and catalyst amount were studied. Allylimidazolium-based ILs on modified silica gels were superior to other tested solid acid catalysts. Especially, the performance of $SiO_2-[ASBI][HSO_4]$ (immobilized by grafting of 3-allyl-1-(4-sulfobutyl)imidazolium hydrogen sulfate on silica gel) was better than that of a widely known Amberlyst-15 catalyst at the same reaction conditions. A high conversion yield of 96% was achieved in the esterification reaction of the simulated cooking oil at 353 K for 2 h. The high catalytic activity of $SiO_2-[ASBI][HSO_4]$ was attributed to the presence of strong Brønsted acid sites from the immobilized functional groups. The catalyst was recovered and the biodiesel product was separated by simple processes such as decantation and filtration.

• Transactions of the Korean Society of Mechanical Engineers B
• /
• v.36 no.8
• /
• pp.873-876
• /
• 2012

Ionic liquids (ILs) existing in the liquid ion form under standard conditions show a unique properties. 1-10-Alkyl-3-methyl-imidazolium bromide ([C10mim][Br]) is one of the ILs that shows amphiphilic characteristics under specific conditions. This property enables it to function as a surfactant, and therefore, it finds applications in a wide range of areas. In this study, we tried to predict the behavior, especially the aggregation aspect, of [C10mim][Br] in an aqueous solution using molecular dynamics (MD) simulations. The canonical (NVT) ensemble was used to relax the system and trace the trajectory of atoms. Several case studies were simulated and the interaction among [C10mim]+, [Br]-, and water was analyzed using the radial distribution function of each atom. The density distribution function was also used for the structural analysis of the entire system. We used the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) code for the present MD simulations.

• Membrane Journal
• /
• v.16 no.4
• /
• pp.268-275
• /
• 2006

Novel SILEMs were prepared by multi-stage phase separation process combined by the low temperature phase separation (LTPS) and the high temperature phase separation (HTPS) using room temperature ionic liquids (RTILs) which have a high ionic conductivity. PVDF and imidazolium series ionic liquids were used as membrane material and electrolyte, respectively. To study the ion conducting properties, the SILEMs were tested using LCR meter at temperature controlled from 30 to $130^{\circ}C$. Under humid conditions, with increasing temperature from 30 to $100^{\circ}C$, the ion conductivity of the cast $Nafion^{(R)}$ membrane increased linearly, but then started to decrease after $100^{\circ}C$. However, in the case of the SILEMs, with increasing operating temperature, the ion conductivity increased. Also, the ion conductivity behaviors of the SILEMs were almost same, regardless of humidity. The ion conductivity of the SILEMs was $2.7{\times}10^{-3}S/cm$ and increased almost linearly up to $2.2{\times}10^{-2}S/cm$ with increasing temperature to $130^{\circ}C$. The effects of an inorganic filler on the physical properties of the SILEMs were studied using the $SiO_2$. The addition of $SiO_2$ could improve the mechanical strength of the SILEMs, though the ionic conductivity was decreased slightly.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.6
• /
• pp.1873-1878
• /
• 2011

Under solvent-free conditions and in one-pot, a series of 2-amino-4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-pyridines and 4-aryl-3-cyano-6-(3,4-dimethoxyphenyl)-2(1H)-pyridinones were prepared using 3,4-dimethoxyacetophenone, an aldehyde, malononitrile (or ethyl cyanoacetate), and ammonium acetate in the presence of 3-methyl-1-(4-sulfonylbutyl)imidazolium hydrogen sulfate $[HO_3S(CH_2)_4MIM][HSO_4]$ (a Br${\o}$nsted acidic ionic liquid) as the catalyst in very short reaction time. The preference for the formation of more stable tautomers was consistence with the theoretical calculation using the Gaussian 03 program at the B3LYP hybrid density functional level.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.6
• /
• pp.1745-1750
• /
• 2013

A novel green aqueous mobile phase modified with room temperature ionic liquids (RTILs) was employed in the absence of volatile organic solvents or ion-pairing reagents to analyze thiamine, a very polar compound, by reverse phase high performance liquid chromatography (RP-HPLC). Due to its strongly hydrophilic nature, thiamine was eluted near the column dead time ($t_0$) using a mobile phase without adding RTILs or ion-pairing reagents, even if a 100% aqueous mobile phase, which has weak elution power under reverse phase conditions, was used. Thus, 1-ethyl-3-methyl-imidazolium hexafluorophosphate ([EMIM][$PF_6$]), which has the strongest chaotropic effect, was selected as a mobile phase additive to improve retention and avoid baseline disturbances at $t_0$. Various mobile phase parameters such as cation moiety, chaotropic anion moiety, pH and concentration of RTILs were optimized to determine thiamine at the proper retention time. Method validation was performed to assess linearity, intra- and inter-day accuracy and precision, recovery and repeatability; all results were found to be satisfactory. The developed method was also compared to the current official United States Pharmacopoeia (USP) and Korean Pharmacopoeia (KP) methods using an organic mobile phase containing an ionpairing reagent by means of evaluating various chromatographic parameters such as the capacity factor, theoretical plate number, peak asymmetry and tailing factor. The results indicated that the proposed method exhibited better efficiency of thiamine analysis than the official methods, and it was successfully applied to quantify thiamine in pharmaceutical preparations.

• Clean Technology
• /
• v.14 no.4
• /
• pp.248-255
• /
• 2008

The volume expansion of three ionic liquids (ILs) in the presence of supercritical carbon dioxide has been measured at pressures up to 32 MPa and at temperatures from 313.15 to 333.15 K in a high-pressure view cell. The imidazolium-derivative ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][$PF_6$]), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][$BF_4$]), and 1-octyl-3-methylimidazolium tetrafluoroborate ([omim][$BF_4$]) were employed in this research. The effects of pressure, temperature, nature of anion and cation as well as the water content on the volume expansion of ILs by absorbing $CO_2$ were investigated experimentally. The volume expansion was higher for the ILs with longer cationic alkyl group and for the ILs with lower anion polarity. The lower the water content, the lower the temperature, or the higher the pressure, the higher was the expansion of IL phase.

• Applied Chemistry for Engineering
• /
• v.25 no.6
• /
• pp.559-563
• /
• 2014

It is well known that $CO_2$ can be dissolved easily in imidazolium-based room temperature ionic liquids (RTILs). Because of the high $CO_2$ solubility in RTILs, membranes containing RTILs can separate easily gas mixtures such as $CO_2/N_2$ and $CO_2/CH_4$. In this study, we prepared poly(vinylidene fluoride)-hexafluoropropyl copolymer (PVDF-HFP) gel membranes with several RTILs and measured permeabilities of several gases. When the anion of ionic liquids was tetrafluoroborate($BF{_4}^-$), both $CO_2$ permeability and selectivities decreased as the carbon number of the cation increased. When the cation of ionic liquids was 1-ethyl-3-methylimidazolium[emim], $CO_2$ permeability of gel membranes containing bis(trifluoromethane) sulfoneimide($Tf_2N^-$) anion was double compared to those containing tetrafluoroborate($BF{_4}^-$) anion. However, $CO_2/N_2$ and $CO_2/CH_4$ selectivities of the $Tf_2N^-$ case were decreased, whereas the $H_2$ selectivity was almost the same for two cases.

• 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.

• Journal of Forest and Environmental Science
• /
• v.36 no.1
• /
• pp.62-66
• /
• 2020

Ethanol fermentation of the enzymatic hydrolysates from the products pretreated using 1-ethyl-3-methyl-imidazolium acetate ([EMIM]Ac) and its co-solvents with dimethylformamide (DMF) was conducted using Saccharomyces cerevisiae (D452-2). The optical density change due to the yeast cell growth, the consumption amount of monosugars (glucose, xylose), the concentration of acetate, and ethanol production yield were investigated. The co-solvent system lowered inhibition of the growth of the cells. The highest concentration of glucose (7.8 g/L) and xylose (3.6 g/L) was obtained from the enzymatic hydrolysates of the pretreated product by pure [EMIM]Ac. The initial concentration of both monosugars in the enzymatic hydrolysates was decreased with increasing fermentation time. Ethanol of Approximately 3 g/L was produced from the enzymatic hydrolysates by pure [EMIM]Ac and co-solvent with less than 50% DMF.