• Korean Chemical Engineering Research
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• v.47 no.5
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• pp.608-614
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• 2009

In this work, ruthenium substituted SBA-15's(Ru-SBA15's) of various Si/Ru ratios were prepared using a non-ionic triblock copolymer surfactant, $EO_{20}PO_{70}EO_{20}$, as template. We investigated the nitrogen or oxygen adsorption/desorption behaviors of the Ru-SBA-15's for their future applications as catalysts or selective adsorbents, etc. The pore size of the Ru-SBA-15's was determined by both the Barrett-Joyner-Halenda(BJH)($D_{BJH}$) and the Broekhoff-de Boer analysis with a Frenkel-Halsey-Hill isotherm(BdB-FFF) method($D_{BdB-FHH}$). The $D_{BJH}$ and $D_{BdB-FHH}$ of the Ru-SBA-15 having 50/1 ratio of Si/Ru were 3.9 nm and 4.7 nm, respectively. The transmission electron microscope(TEM) image of the Ru-SBA 15 of the Si/Ru mole ratio of 50 showed that the pore size is 4.7 nm, which is consistent with the $N_2$ adsorption results with the BdB-FHH method. The surface area of pores form oxygen adsorption/desorption isotherm was higher than that from the nitrogen adsorption/desorption isotherm by the Brunauer-Emmett-Teller(BET) method, which were respectively $612.7m^2/g$, and $573.3m^2/g$. X-ray diffraction(XRD) patterns and TEM analyses showed that the mesoporous materials possess well-ordered hexagonal arrays.

• Journal of the Korean Chemical Society
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• v.46 no.1
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• pp.57-63
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• 2002

The hydropurification reaction of CTA (crude terephthalic acid) was carried out with hydrogen over PdRu/CCM (carbon-carbonaceous composite material) catalyst in a batch reactor at high temperature. The first order kinetics of hydropurification is confirmed with the linear dependence of ln(4-CBA; 4-carboxybenzaldehyde) with reaction time. The reaction condition studied is thought to represent the hydropurification well because of the linear dependence of catalytic activity on the catalyst weight. The p-toluic acid (p-tol) in solid and liquid increases with the conversion of reaction or the decrease of 4-CBA. However, the benzoic acid (BA) concentration does not depend much on the conversion. The AT (alkali transmittance) does not depend on the 4-CBA when the concentration is higher than about 0.2% which shows the 4-CBA, in itself, does not cause the coloring effect. The AT of PTA depends inversely with the concentration of 4-CBA when the 4-CBA is less than about 0.15%. This may show the coloring materials are removed in parallel with the hydrogenation of 4-CBA. The (0.3%Pd-0.2%Ru)/CCM shows larger residual catalytic activity than a commercial catalyst, 0.5%Pd/C, after using in a commercial reactor even though the former has smaller fresh activity than the latter. The palladium and ruthenium in PdRu/CCM show the synergetic effect in activity when the ruthenium concentration is about $0.2{\sim}0.35$ wt%. It may be supposed that the PdRu/CCM catalyst can be a promising candidate to replace the commercial Pd/C catalyst.

• The Korean Journal of Physiology and Pharmacology
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• v.15 no.1
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• pp.53-59
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• 2011

The secretion of insulin from pancreatic ${\beta}$-cells is triggered by the influx of $Ca^{2+}$ through voltage-dependent $Ca^{2+}$ channels. The resulting elevation of intracellular calcium ($[Ca^{2+}]_i$) triggers additional $Ca^{2+}$ release from internal stores. Less well understood are the mechanisms involved in $Ca^{2+}$ mobilization from internal stores after activation of $Ca^{2+}$ influx. The mobilization process is known as calcium-induced calcium release (CICR). In this study, our goal was to investigate the existence of and the role of caffeine-sensitive ryanodine receptors (RyRs) in a rat pancreatic ${\beta}$-cell line, INS-1 cells. To measure cytosolic and stored $Ca^{2+}$, respectively, cultured INS-1 cells were loaded with fura-2/AM or furaptra/AM. $[Ca^{2+}]_i$ was repetitively increased by caffeine stimulation in normal $Ca^{2+}$ buffer. However, peak $[Ca^{2+}]_i$ was only observed after the first caffeine stimulation in $Ca^{2+}$ free buffer and this increase was markedly blocked by ruthenium red, a RyR blocker. KCl-induced elevations in $[Ca^{2+}]_i$ were reduced by pretreatment with ruthenium red, as well as by depletion of internal $Ca^{2+}$ stores using cyclopiazonic acid (CPA) or caffeine. Caffeine-induced $Ca^{2+}$ mobilization ceased after the internal stores were depleted by carbamylcholine (CCh) or CPA. In permeabilized INS-1 cells,$Ca^{2+}$ release from internal stores was activated by caffeine, $Ca^{2+}$, or ryanodine. Furthermore, ruthenium red completely blocked the CICR response in perrneabilized cells. RyRs were widely distributed throughout the intracellular compartment of INS-1 cells. These results suggest that caffeine-sensitive RyRs exist and modulate the CICR response from internal stores in INS-1 pancreatic ${\beta}$-cells.

• Journal of the Korean Chemical Society
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• v.54 no.3
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• pp.261-268
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• 2010

In this account, three synthetic methodologies that serve as the basis for new strategies for the preparation of selected natural products are briefly introduced. One process, involving ruthenium carbene catalyzed ring rearrangement metathesis developed by Grubbs and his coworkers, transforms alkene-tethered cycloalkenes to thermodynamically more favored alkene-tethered cycloalkenes. Another ruthenium carbene promoted reaction, referred to as dienyne metathesis, was uncovered in early studies by Grubbs and his collaborators. This process converts dienynes to fused bicyclic conjugated dienes. Finally, a novel photo-electrocyclization reaction of pyridinium salts, which leads to the formation of 4-aminocyclopenten-3,5-diol derivatives, is discussed. Examples are provided to show the utility of these methodologies in natural product synthesis. Emphasis is given to studies in which pyridinium salt photochemistry is coupled with ring rearrangement and dienyne metathesis in routes for the synthesis of polyhydroxyalted indolizidine alkaloids and the construction of the tricyclic core of the lepadiformine and cylindricine alkaloids.

• Journal of the Korean Chemical Society
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• v.37 no.11
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• pp.967-973
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• 1993

${\alpha},{\omega}$-Diols such as 1,6-hexanediol and 1,7-heptanediol react with secondary amines in the presence of catalytic amount of ruthenium complex at 180$^{\circ}$C for 24 hrs to give the corresponding diamino compounds in good yields. The yield of diamino compound was affected by the molar ratio of ${\alpha},{\omega}$-diol to secondary amine. The reaction was also affected by the nature of the phosphorus ligands employed. On the other hand, aromatic primary amines react with 1,2,6-hexanetriol in the presence of RuCl_3{\cdot}H_2O-3PPh_3$ at 180$^{\circ}$C for 3 hours under argon atmosphere to give selectively 1-substituted aryl-3-hydroxyperhydroazepines in good yields. Selective synthesis of these products show that two primary hydroxy groups (1,6-positions) oxidize predominantly than secondary hydroxy group (2-position) by ruthenium-phosphorus complex. The yields were decreased according to the order of para-, meta- and ortho-substituent.

• Journal of Adhesion and Interface
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• v.19 no.1
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• pp.13-18
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• 2018

At ruthenium (Ru) catalyst was exposed from the atmosphere, the degree of catalyst activation decreased. The change of catalyst activity with the number of days of exposure to air for the Ru catalyst was confirmed using the surface tension method quantitatively. Mechanical properties and surfactant change after polymerization by DCPD using Ru catalyst for each air exposure day was evaluated. The Ru catalyst mixed with a dilution agent was exposed in the air and color was monitored for each day. Surface tension was measured using Wilhelmy and PTFE and associated with different catalyst activities. Heat was measured in real time during polymerizing DCPD with Ru catalyst. After polymerization, tensile strength was measured for p-DCPD and the change of material property was measured. Interfacial properties were also evaluated via microdroplet pull-out tests between glass fiber and p-DCPD. The surface tension was stable until the 4 days (33 dyne/cm) whereas the surface energy increased at the 10 days (34 dyne/cm), which could be correlated with oxidation of the catalyst. Tensile property and interfacial shear strength (IFSS) was also stable until the 4 days (tensile strength: 38 MPa and IFSS: 26 MPa) whereas the mechanical property decrease at 10 days (tensile strength: 15 MPa and IFSS: 3 MPa) dramatically.

• The Korean Journal of Pharmacology
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• v.31 no.2
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• pp.207-217
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• 1995

To investigate the functional and immunological properties of the Ca-release channel in the sarcoplasmic reticulum(SR) of the eel skeletal muscle, $[^3H]ryanodine$ binding, SDS gel electrophoresis, $^{45}Ca\;release$ studies, and immunoblot assay were carried out in the SR of the eel skeletal muscle. Maximal binding sites(Bmax) and $K_D$ values of $[^3H]ryanodine$ for Ca-release channel of the SR of the eel skeletal muscle were $19.44{\pm}1.40\;pmole/mg$ protein and $15.55{\pm}1.69\;nM$, respectively. $[^3H]Ryanodine$ binding to RyR was increased by calcium and AMP. The SR of the eel skeletal muscle has two high molecular weight bands on the SDS PAGE. The mobility of upper band was more slower than the single band of the rabbit skeletal muscle, and that of the lower band was similar with the single band of canine cardiac muscle. Vesicular $^{45}Ca-release$ was activated by calcium. Ca-induced $^{45}Ca-release$ was significantly inhibited by $MgCl_2(2\;mM)$, ruthenium red$(10\;{/mu}M)$ or tetracaine(1 mM), but not by high concentration of calcium itself. AMP-induced $^{45}Ca-release$ was slightly occurred only in the absence of calcium, it was not inhibited by $MgCl_2$ or ruthenium red. Caffeine also increased $^{45}Ca-release$ from the SR vesicles, but it was not affected by $MgCl_2$ or ruthenium red. Polyclonal Ab against rat skeletal muscle RyR is reacted with that of rabbit, but not reacted with that of the eel skeletal muscle. These results suggested that ryanodine receptor of the SR of the eel skeletal muscle is showing some similar properties with that of mammalian skeletal muscle, but might be an another isotype channel having two bands which is less sensitive to AMP, not cross-reacted with antisera against rat RyR, and not inhibited by high concentration of calcium.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.78-78
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• 2013

Recently, many platinoid metals like platinum and ruthenium have been used as an electrode of microelectronic devices because of their low resistivity and high work-function. However the material cost of Ru is very expensive and it usually takes long initial nucleation time on SiO2 during chemical deposition. Therefore many researchers have focused on how to enhance the initial growth rate on SiO2 surface. There are two methods to deposit Ru film with atomic layer deposition (ALD); the one is thermal ALD using dilute oxygen gas as a reactant, and the other is plasma enhanced ALD (PEALD) using NH3 plasma as a reactant. Generally, the film roughness of Ru film deposited by PEALD is smoother than that deposited by thermal ALD. However, the plasma is not favorable in the application of high aspect ratio structure. In this study, we used a bis(ethylcyclopentadienyl)ruthenium [Ru(EtCp)2] as a metal organic precursor for both thermal and plasma enhanced ALDs. In order to reduce initial nucleation time, we use several methods such as Ar plasma pre-treatment for PEALD and usage of sacrificial RuO2 under layer for thermal ALD. In case of PEALD, some of surface hydroxyls were removed from SiO2 substrate during the Ar plasma treatment. And relatively high surface nitrogen concentration after first NH3 plasma exposure step in ALD process was observed with in-situ Auger electron spectroscopy (AES). This means that surface amine filled the hydroxyl removed sites by the NH3 plasma. Surface amine played a role as a reduction site but not a nucleation site. Therefore, the precursor reduction was enhanced but the adhesion property was degraded. In case of thermal ALD, a Ru film was deposited from Ru precursors on the surface of RuO2 and the RuO2 film was reduced from RuO2/SiO2 interface to Ru during the deposition. The reduction process was controlled by oxygen partial pressure in ambient. Under high oxygen partial pressure, RuO2 was deposited on RuO2/SiO2, and under medium oxygen partial pressure, RuO2 was partially reduced and oxygen concentration in RuO2 film was decreased. Under low oxygen partial pressure, finally RuO2 was disappeared and about 3% of oxygen was remained. Usually rough surface was observed with longer initial nucleation time. However, the Ru deposited with reduction of RuO2 exhibits smooth surface and was deposited quickly because the sacrificial RuO2 has no initial nucleation time on SiO2 and played a role as a buffer layer between Ru and SiO2.

• Clean Technology
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• v.28 no.3
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• pp.232-237
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• 2022

Biorefineries, in which renewable resources are utilized, are an eco-friendly alternative based on biomass feedstocks. Alginic acid, a major component of brown algae, which is a type of marine biomass, is widely used in various industries and can be converted into value-added chemicals such as sugars, sugar alcohols, furans, and organic acids via catalytic hydrothermal decomposition under certain conditions. In this study, ruthenium-supported activated carbon and magnesium oxide were mixed and applied to the depolymerization of alginic acid in a batch reactor. The addition of magnesium oxide as a basic promoter had a strong influence on product distribution. In this heterogeneous catalytic system, the separation and purification processes are also simplified. After the reaction, low molecular weight alcohols and organic acids with 5 or fewer carbons were produced. Specifically, under the optimal reaction conditions of 30 mL of 1 wt% alginic acid aqueous solution, 100 mg of ruthenium-supported activated carbon, 100 mg of magnesium oxide, 210 ℃ of reaction temperature, and 1 h of reaction time, total carbon yields of 29.8% for alcohols and 43.8% for a liquid product were obtained. Hence, it is suggested that this catalytic system results in the enhanced hydrogenolysis of alginic acid to value-added chemicals.

• Bulletin of the Korean Chemical Society
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• v.23 no.1
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• pp.13-14
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• 2002