1H NMR Measurements of the Phase Transition of (NH₄)₃H(SO₄)₂ Single Crystals

S. H. Choi,Moohee Lee,Ae Ran Lim,K. S. Han,S. K. Kwon,S. K. Nam 한국물리학회 2008 THE JOURNAL OF THE KOREAN PHYSICAL SOCIETY Vol.52 No.2

$^1$H nuclear magnetic resonance (NMR) experiments have been performed in the temperature range of 30 -- 300 K at 7 T to investigate the phase-dependent nature of the dynamic network of hydrogen bonds in a ((NH₄)₃H(SO₄)₂ single crystal. The crystal has six phases, which are ferroelectric, antiferroelectric, incommensurate, antiferroelectric, ferroelastic, and superionic with the respective transition temperatures of 63, 133, 139, 256 and 413 K. The spin-lattice relaxation time, T₁, of ¹H NMR is similar for the ammonium protons and the hydrogen-bond protons over the entire range of experimental temperatures. The T₁, of ¹H NMR gradually decreases down to 120 K and starts to steeply increase below 100 K. Then, the T₁ shows an abrupt decrease below 68 K with a sharp minimum at 63 K, where the ferroelectric transition occurs. The ¹H NMR spectrum shifts to the high-frequency side at temperatures below 63 K due to the ferroelectric phase transition. This behavior of the T₁ and the spectrum confirms a dramatic change in the dynamics of hydrogen bonds associated with the ferroelectric phase transition at 63 K. $^1$H nuclear magnetic resonance (NMR) experiments have been performed in the temperature range of 30 -- 300 K at 7 T to investigate the phase-dependent nature of the dynamic network of hydrogen bonds in a ((NH₄)₃H(SO₄)₂ single crystal. The crystal has six phases, which are ferroelectric, antiferroelectric, incommensurate, antiferroelectric, ferroelastic, and superionic with the respective transition temperatures of 63, 133, 139, 256 and 413 K. The spin-lattice relaxation time, T₁, of ¹H NMR is similar for the ammonium protons and the hydrogen-bond protons over the entire range of experimental temperatures. The T₁, of ¹H NMR gradually decreases down to 120 K and starts to steeply increase below 100 K. Then, the T₁ shows an abrupt decrease below 68 K with a sharp minimum at 63 K, where the ferroelectric transition occurs. The ¹H NMR spectrum shifts to the high-frequency side at temperatures below 63 K due to the ferroelectric phase transition. This behavior of the T₁ and the spectrum confirms a dramatic change in the dynamics of hydrogen bonds associated with the ferroelectric phase transition at 63 K.

Expression and N-glycan analysis of human 90K glycoprotein in Drosophila S2 cells

Kim, K.R.,Kim, Y.K.,Cheong, H.,Kim, J.Y.H.,Cha, H.J. IPC Science and Technology Press ; Elsevier Scienc 2013 Enzyme and microbial technology Vol.53 No.3

Human 90K (h90K; Mac-2-binding protein) glycoprotein is a potential pharmaceutical due to its inhibitory activity against cancer metastasis and expansion. Here, h90K glycoprotein was produced in insect Drosophila S2 cell system, and its N-glycan pattern was analyzed. A plasmid encoding h90K gene, fused with a hexahistidine tag under the control of Drosophila metallotionein promoter, was stably transfected into S2 cells. After copper sulfate induction, transfected S2 cells secreted recombinant h90K at a good expression level of 28mg/L in a 150-mL spinner flask culture. The purified recombinant h90K showed an apparent molecular weight of ~78kDa which was much smaller than that (~97kDa) of the natural h90K. Because de-N-glycosylated h90K appeared at ~60kDa protein band, it was suggested that the recombinant h90K from S2 cells has small N-glycans with about half the molecular weight (~18kDa) of N-glycans of the natural h90K. Through detail analyses using high-performance liquid chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, the S2-derived recombinant h90K was confirmed that it has simple paucimannosidic structures containing two or three mannose residues with core fucose as the major (~79%) N-glycans.

[ $^1H$ ] Nuclear Magnetic Resonance Study of Ferroelectric $(NH_4)_3H(SO_4)_2$

Choi, S.H.,Han, K.S.,Kwon, S.K.,Nam, S.K.,Choi, H.H.,Lee, Moo-Hee,Lim, Ae-Ran Korean Magnetic Resonance Society 2007 Journal of the Korean Magnetic Resonance Society Vol.11 No.2

[ $^1H$ ] nuclear magnetic resonance (NMR) experiments have been performed at 30 - 300 K and 7 T to investigate dynamics of hydrogen bond network in the single crystal $(NH_4)_3H(SO_4)_2$. The two proton sites, ammonium proton and hydrogen-bond proton, are identified from the $^1H$ NMR MAS spectrum at 340 K. As temperature decreases, the $^1H$ NMR spectrum shifts to the higher frequency side with a larger linewidth. The spectrum at 65 K shows a distinctive change in line shape toward the ferroelectric transition at 63 K. The measured values of $T_1$ for ammonium and hydrogen-bond protons are similar in the whole range of temperature. $T_1$ of $^1H$ NMR shows a gradual decrease down to 120 K and starts to steeply increase below 100 K. Then $T_1$ shows abrupt decrease below 70 K with a sharp minimum at 63 K, where the ferroelectric transition occurs. This temperature dependence of spectrum and $T_1$ clearly prove that the large change in the dynamics of hydrogen bond network is associated with the ferroelectric phase transition at 63 K.

1H Nuclear Magnetic Resonance study of Ferroelectric (NH4)3H(SO4)2

S. H. Choi,K. S. Han,S. K. Kwon,S. K. Nam,H. H. Choi,Moohee Lee,Ae Ran Lim 한국자기공명학회 2007 Journal of the Korean Magnetic Resonance Society Vol.11 No.2

1H nuclear magnetic resonance (NMR) experiments have been performed at 30 - 300 K and 7 T to investigate dynamics of hydrogen bond network in the single crystal (NH4)3H(SO4)2. The two proton sites, ammonium proton and hydrogen-bond proton, are identified from the 1H NMR MAS spectrum at 340 K. As temperature decreases, the 1H NMR spectrum shifts to the higher frequency side with a larger linewidth. The spectrum at 65 K shows a distinctive change in line shape toward the ferroelectric transition at 63 K. The measured values of T1 for ammonium and hydrogen-bond protons are similar in the whole range of temperature. T1 of 1H NMR shows a gradual decrease down to 120 K and starts to steeply increase below 100 K. Then T1 shows abrupt decrease below 70 K with a sharp minimum at 63 K, where the ferroelectric transition occurs. This temperature dependence of spectrum and T1 clearly prove that the large change in the dynamics of hydrogen bond network is associated with the ferroelectric phase transition at 63 K.

Induction of Cell Death in Human Macrophages by a Highly Virulent Korean Isolate of <i>Mycobacterium tuberculosis</i> and the Virulent Strain H37Rv

Sohn, H.,Lee, K.-S.,Kim, S.-Y.,Shin, D.-M.,Shin, S.-J.,Jo, E.-K.,Park, J.-K.,Kim, H.-J. Blackwell Publishing Ltd 2009 Scandinavian journal of immunology Vol.69 No.1

<P>Abstract</P><P>Recent studies have suggested that virulent strains of <I>Mycobacterium tuberculosis</I> induce apoptosis in macrophages less often than do attenuated strains. K-strain, which belongs to the Beijing family, is the most frequently isolated clinical strain of <I>M. tuberculosis</I> in Korea. In this study, we investigated the differential induction of cell death in human monocytic THP-1 cells by K-strain and H37Rv, a virulent but laboratory-adapted strain of <I>M. tuberculosis</I>. Although no significant difference in growth rate was observed between the cells exposed to K-strain and those exposed to H37Rv, the levels of protective cytokines such as tumour necrosis factor (TNF)-&agr;, interleukin (IL)-6 and IL-12p40 were lower in K-strain-infected cells than in H37Rv-infected cells. Cell viability assays showed that both K-strain and H37Rv, but not heat- or streptomycin-killed bacteria, induced THP-1 cell death in a TNF-independent manner. In contrast, double staining with fluorochrome-labelled inhibitors of caspase and propidium iodide and lactate dehydrogenase release assays revealed that K-strain induced significantly higher levels of necrotic cell death, rather than apoptosis, in THP-1 cells than did H37Rv. Anti-apoptotic <I>Bcl-2</I>, <I>Mcl-1</I>, <I>Bfl-1</I> and <I>Bcl-xL</I> in the cells were significantly upregulated following infection with K-strain compared with H37Rv, whereas <I>Bax</I> was slightly upregulated in response to infection with both H37Rv and K-strain. These results suggest that the highly virulent K-strain keeps cellular apoptosis as a host defense mechanism to a minimum and induces necrosis in macrophages.</P>

Proposed mechanism in the change of cellular composition in the outer medullary collecting duct during potassium homeostasis.

Park, E-Y,Kim, W-Y,Kim, Y-M,Lee, J-H,Han, K-H,Weiner, I D,Kim, J Gutenberg 2012 HISTOLOGY AND HISTOPATHOLOGY Vol.27 No.12

<P>Potassium depletion (K?-D) induces hypertrophy and hyperplasia of collecting duct cells, and potassium repletion (K?-R) induces regression of these changes. The purpose of this study was to examine the time courses of the changes in cellular composition, the origin of intercalated cells (ICs) and the mechanism responsible for these changes. SD rats received K?-depleted diets for 1, 7, or 14 days. After K?-D for 14 days some of the rats received normal diets for 1, 3, 5, or 7 days. In the inner stripe of the outer medulla, K?-D increased significantly the number and proportion of H?-ATPase-positive ICs, but decreased the proportion of H?-ATPase-negative principal cells (PCs). However, proliferation was limited to H?-ATPase-negative PCs. During K?-R, the cellular composition was recovered to control level. Apoptosis increased during K?-R and exclusively limited in H?-ATPase-negative PCs. Double immunolabeling with antibodies to PC and IC markers identified both cells negative or positive for all markers during both K?-D and K?-R. Electron microscopic observation showed that ultrastructure of AE1-positive some cells were similar to AE1-negative some cells during K?-R. LC3 protein expression increased significantly and autophagic vacuoles appeared particularly in PCs on days 14 of K?-D and in ICs on days 3 of K?-R. These results suggest that PCs and ICs may interconvert in response to changes in dietary K+ availability and that autophagic pathways may be involved in the interconversion.</P>

Determination of the Langmuir and Temkin Adsorption Isotherms of H for the Cathodic H₂ Evolution Reaction at a Pt/KOH Solution Interface Using the Phase-Shift Method

Chun Jang-H.,Jeon Sang-K.,Chun Jin-Y. The Korean Electrochemical Society 2006 한국전기화학회지 Vol.9 No.1

The phase-shift method for determining the Langmuir, Frumkin, and Temkin adsorption isotherms ($\theta_H\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at a Pt/0.1 M KOH solution interface has been proposed and verified using cyclic voltammetric, differential pulse voltammetric, and electrochemical impedance techniques. At the Pt/0.1 M KOH solution interface, the Langmuir and Temkin adsorption isotherms ($\theta_H\;vs.\;E$), the equilibrium constants ($K_H=2.9X10^{-4}mol^{-1}$ for the Langmuir and $K_H=2.9X10^{-3}\exp(-4.6\theta_H)mol^{-1}$ for the Temkin adsorption isotherm), the interaction parameters (g=0 far the Langmuir and g=4.6 for the Temkin adsorption isotherm), the rate of change of the standard free energy of $\theta_H\;with\;\theta_H$ (r=11.4 kJ $mol^{-1}$ for g=4.6), and the standard free energies (${\Delta}G_{ads}^{\circ}=20.2kJ\;mol^{-1}$ for $k_H=2.9\times10^{-4}mol^{-1}$, i.e., the Langmuir adsorption isotherm, and $16.7<{\Delta}G_\theta^{\circ}<23.6kJ\;mol^{-1}$ for $K_H=2.9\times10^{-3}\exp(-4.6\theta_H)mol^{-1}$ and $0.2<\theta_H<0.8$, i.e., the Temkin adsorption isotherm) of H for the cathodic HER are determined using the phase-shift method. At intermediate values of $\theta_H$, i.e., $0.2<\theta_H<0.8$, the Temkin adsorption isotherm ($\theta_H\;vs.\;E$) corresponding to the Langmuir adsorption isotherm ($\theta_H\;vs.\;E$), and vice versa, is readily determined using the constant conversion factors. The phase-shift method and constant conversion factors are useful and effective for determining the Langmuir, Frumkin, and Temkin adsorption isotherms of intermediates for sequential reactions and related electrode kinetic and thermodynamic data at electrode catalyst interfaces.

The Phase-Shift Method for the Langmuir Adsorption Isotherms of Electroadsorbed Hydrogens for the Cathodic H₂ Evolution Reactions at the Poly-Pt Electrode Interfaces

천장호,전상규,이재항,Chun, Jang H.,Jeon, Sang K.,Lee, Jae H. The Korean Electrochemical Society 2002 한국전기화학회지 Vol.5 No.3

순환전압전류 및 교류임피던스 기법을 이용하여 다결정 Pt/0.5M $H_2SO_4$ 및 0.5M LiOH수용액 계면에서 저전위 수소흡착(UPD H) 과 전위 수소흡착(OPD H)에 관한 Langmuir 흡착등온식 $({\theta}\;vs.\;E)$ 을 연구조사 하였다. 계면에서 치적중간주파수일 때 위상이동$(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ 거동은 표면피복율$(1{\geq}{\theta}{\geq}0)$ 거동에 정확하게 상응한다. 위상이 동 방법 즉 최적중간주파수일 때 위상이동 변화$({-\phi}\;vs.\;E)$는 계면에서 음극 $H_2$ 발생 반응에 관한 UPD H와 OPDH의 Langmuir흡착등온식을 결정할 수 있는 새로운 전기화학적 방법으로 사용할 수 있다 다결정 Pt/0.5M $H_2SO_4$ 수용액 계면에서 OPD H의 흡착평형상수(K)와 표준자유에너지$({\Delta}G_{ads})$는 각각 $2.1\times10^{-4}$와 21.0kJ/mol 이다. 다결정 Pt/0.5M LiOH 수용액 계면에서 K는 음전위(E)에 따라 2.7 (UPD H)에서 $6.2\times10^{-6}$ (OPD H) 또는 $6.2\times10^{-6}$(OPD H)에서 2.7 (UPD H)로 전이한다. 유사하게 ${\Delta}G_{ads}$는 E에 따라 -2.5kJ/mol (UPD H)에서 29.7kJ/mol (OPD H)또는 29.7kJ/mol (OPD H)에서 -2.5kJ/mol (UPD H)로 전이한다. K와 ${\Delta}G_{ads}$의 전이는 다결정 Pt전극 표면의 상이한 UPD H와 OPD H의 흡착부위에 기인한다. 다결정 Pt전극 계면에서 UPD H와 OPD H는 음극 $H_2$ 발생 반응에 따른 순차적 과정이 아니라, 수소 흡착부위 자체에 따른 독립적 과정이다. UPD H와 OPD H의 기준은 음극 $H_2$발생 반응과 전위가 아니라, 수소 흡착부위와 과정이다. 수용액에서 음극 $H_2$발생 반응에는 다결정 Pt선 전극이 단결정 Pt(100)원반 전극보다 더 효율적이고 유용하다 위상이동 방법은 열역학적 방법과 상충적이 아니라, 보완적이다. The Langmuir adsorption isotherms of the under-potentially deposited hydrogen (UPD H) and the over-potentially deposited hydrogen (OPD H) at the poly-Pt/0.5M $H_2SO_4$ and 0.5 M LiOH aqueous electrolyte interfaces have been studied using cyclic voltammetric and ac impedance techniques. The behavior of the phase shift $(0^{\circ}{\leq}{-\phi}{\leq}90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1{\geq}{\theta}{\geq}0)$ at the interfaces. The phase-shift method, i.e., the phase-shift profile $({-\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new electrochemical method to determine the Langmuir adsorption isotherms $({\theta}\;vs.\;E)$ of the UPD H and the OPD H for the cathodic $H_2$ evolution reactions at the interfaces. At the poly-Pt/0.5M $H_2SO_4$ aqueous electrolyte interface, the equilibrium constant (K) and the standard free energy $({\Delta}G_{ads})$ of the OPD H are $2.1\times10^{-4}$ and 21.0kJ/mol, respectively. At the poly-Pt/0.5M LiOH aqueous electrolyte interface, K transits from 2.7(UPD H) to $6.2\times10^{-6}$ (OPD H) depending on the cathode potential (E) and vice versa. Similarly, ${\Delta}G_{ads}$ transits from -2.5kJ/mol (UPD H) to 29.7kJ/mol (OPD H) depending on I and vice versa. The transition of K and ${\Delta}G_{ads}$ is attributed to the two distinct adsorption sites of the UPD H and the OPD H on the poly-Pt surface. The UPD H and the OPD H on the poly-Pt surface are the independent processes depending on the H adsorption sites themselves rather than the sequential processes for the cathodic $H_2$ evolution reactions. The criterion of the UPD H and the OPD H is the H adsorption sites and processes rather than the $H_2$ evolution reactions and potentials. The poly-Pt wire electrode is more efficient and useful than the Pt(100) disc electrode for the cathodic $H_2$ evolution reactions in the aqueous electrolytes. The phase-shift method is well complementary to the thermodynamic method rather than conflicting.

On the zeolitic imidazolate framework-8 (ZIF-8) membrane for hydrogen separation from simulated biomass-derived syngas

Yin, H.,Lee, T.,Choi, J.,Yip, A.C.K. Elsevier 2016 Microporous and mesoporous materials Vol.233 No.-

<P>Hydrogen separation from biomass-derived syngas is a critical step in the utilization of gasification technology. Compared with the traditional methods, membrane technology provides an effective and low-cost solution for adjusting the gas composition and collecting H-2 in syngas environments. In this study, a zeolitic imidazolate framework-8 (ZIF-8)-based membrane, which is a potential candidate for H-2 separation from biomass-derived syngas, was successfully fabricated through the seeded (secondary) growth method and the subsequent post-treatments. The prepared ZIF-8 membrane exhibited a modest H-2 separation performance for H-2/CO2 and H-2/CO, with separation factors of 4.95 and 6.08, respectively, and a H-2 permeance of 7.81 x 10(-8) mol m(-2) s(-1) Pa-1 at 200 degrees C in the simulated biomass-derived syngas environments (H-2/CO2/CO) with the presence of steam. In particular, the H-2/CO2 and H-2/CO separation factors were increased by 36% and 97%, respectively, with respect to those obtained through bare supports. Despite the promising H2 perm-selectivity, the H-2/CO2 and H-2/CO separation factors of ZIF-8 membranes at 200 degrees C under water-containing syngas environments were maintained up to 10 h but the longer exposure led to the gradual degradation and eventual reduction toward those of bare supports after 15 h seemingly due to the water-involved membrane degradation. This study provides the availability and limitation of ZIF-8 membranes for H-2 separations in stimulated biomass-derived syngas environments. (C) 2015 Elsevier Inc. All rights reserved.</P>

Relationship between Stress Gene Polymorphisms and Litter Size by AI in Pigs

H. J. Jin,I. C. Kim,M. S. Wee,S. H. Yeon,C. D. Kim,S. S. Lee,C. Y. Cho,S. R. Cho,D. S. Son,C. K. Park,Z. D. Li 사단법인 한국동물생명공학회 2007 한국동물생명공학회지 Vol.22 No.4

This study was performed to investigate the relationship between PSS-HSP70 gene polymorphism and artificial insemination (AI) reproductivity in the pigs. The RFLP polymorphism of PSS and the SSCP polymorphisms of HSP70 K1, K3 and K4 PCR product were detected different patterns. In the experiment for AI of fresh semen, spring and fall season showed higher litter size born of 10.89 head than 10.47 head of summer season. Landrace was showed higher litter size of 9.96 head than that of Duroc and Yorkshire(p<0.05). Stress relating PSS and HSP70 polymorphism of PSS-Normal, HSP70 K1-BB, K3-AB, K4-AA showd a highest litter size born of 10.97 head and litter size born alive of 10.69 head than that of the other polymorphisms(p<0.05). In the experiment for AI of frozen semen, effects of season and pig breeds were not showed for litter size born. The stress relating polymorphism of PSS-Carrier, HSP70 K1-BB, K3-BB, K4-AB showed highest litter size born of 11.29 head and litter size born alive of 10.82 head and PSS-Normal, HSP70 K1-BB, K3-AB, K4-AA showed the lowest litter size born of 8.48 head and litter size born alive of 7.33 head than that of the other polymorphisms(p<0.05). These results suggest that AI litter size born for the stress of forzen thawed semen may be affected by PSS and HSP70 polymorphism in pigs.