• Title/Summary/Keyword: $S_N1$ mechanism

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UV Resonance Raman Studies of Cis-Peptide, Diketopiperazine (자외선 공명 라만분광법을 이용한 시스-펩티드, 디케토피페라진 연구)

  • Song, Sunho
    • Analytical Science and Technology
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    • v.6 no.1
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    • pp.39-45
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    • 1993
  • We have examined Raman spectra of cis-peptide model complex, diketopiperazine in water and $D_2O$ with 320 nm through 218 nm excitation. Our study examines assignment of the resonance enhanced amide vibrations and characterizes their enhancement mechanism. Three resonance enhaned cis-peptide marker bands were observed in aqueous solution at 1676, 1533 and $806cm^{-1}$, which were assigned to the cis-amide I, II and S band, respectively. The $1533cm^{-1}$ amide II band, which is almost pure C-N stretching, was most dominant in water and shifted to $1520cm^{-1}$ upon N-deuteration. This band will be probably a potential probe band for cis-peptide moieties in proteins. The excitation profile data and an Albrecht A-term fit indicated that the cis-peptide vibrations derive their intensities from the 188 nm cis-peptide ${\pi}-{\pi}^*$ electronic transition. We Propose that the geometry of cis-peptide ${\pi}^*$ excited state is C-N bond displacement relative to that of electronic ground state.

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Phenomenological Study on Crystal Phase Separation in InGaN/GaN Multiple Quantum Well Structures (InGaN/GaN 다중 양자우물 구조에서의 결정상 분리 현상 연구)

  • Lee, S.J.;Kim, J.O.;Kim, C.S.;Noh, S.K.;Lim, K.Y.
    • Journal of the Korean Vacuum Society
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    • v.16 no.1
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    • pp.27-32
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    • 2007
  • We have investigated photoluminescence(PL) spectra of four $In_xGa_{1-x}N(x=0.15)/GaN$ multiple quantum well(MQW) structures with different well widths in order to study a phenomenon on crystal phase separation. The asymmetic behavior of PL spectra becomes stronger with increase of the well width from 1.5 nm to 6.0 nm, which indicates dual-peak nature. Analyzing the dual-peak fit PL spectra, we have observed that the intensity of low-energy shoulder peak rapidly becomes stronger, compared to that of high-energy peak corresponding to a transition in InGaN QW. It suggests that InGaN QW has two phases with tiny different In compositions, and that In-rich(InN-like) phase forms more and more relatively than stoichiometric InGaN(x=0.15) phase by the InN phase separation mechanism as the QW width increases. PL spectrum of 6.0-nm sample shows an additional peak at low-energy lesion(${\sim}2.0\;eV$) whose energy position is almost the same as a defect band of yellow luminescence frequently observed in GaN epilayers. It may be due to a defect resulted from In deficiency formed with development of the phase separation.

Effects of Different Dietary Oil and d-Limonene on Histopathological and Biochemical Changes in Experimental Hepatocarcinogenesis (식이지방의 종류 및 d-Limonene 투여가 간 발암과정에 미치는 영향)

  • 이미숙;김정희
    • Journal of Nutrition and Health
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    • v.33 no.1
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    • pp.23-32
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    • 2000
  • The purpose of this study was to investigate the effcts of n-3, n-6 fatty arid and d-limonene on histopathological and biochemical changes in experimental rat hepatocarcinogenesis. To attain the above objectives, weanling Sprague-Dawley female rats were intraperitoneally injected twice with a dose of diethylnitrosamine(DEN, 50mg/kg body weight) and after 1 week 0.05% phenobarbital was provided with water. Sardine oil rich in n-3 fatty acids and corn oil rich in n-6 fatty acids were fed at 15% by weight and 5% d-limonene was added to the diet in each group. Ten weeks or 20 weeks after DEN treatment, rats were sacrifirced. The formation of glutathione S-transferase placental form positive(GST-P$\^$+/) foci was significantly decreased by the treatment of either sardine oil or d-limonene HMG-CoA reductase activity was not affected by dietary oils and d-limonene. Protein kinase C (PKC) activity was decreased by either sardine oil or d-limonene. Particularly d-limonene decreased the membrane PKC activity. Membrane Cholesterol/Phospholipid(Chol/PL) ratio was significantly decreased by d-limonene in sardine oil group. The data showed that GST-P$\^$+/ foci number was positively correlated with membrane PKC activity and serum cholesterol and negatively correlated with liver cholesterol level. These results suggest informations about the correlation between histopathological and biochemical changes such as cholesterol metabolism and PKC activity in experimental hepatocarcinogenesis and thereby can elucidate the possible mechanism related to the cancer inhibition.(Korean J Nutrition 33(1) : 23-32, 2000)

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Kinetics and Mechanism of the Anilinolyses of O-Methyl, O-Propyl and O-Isopropyl Phenyl Phosphonochloridothioates in Acetonitrile

  • Barai, Hasi Rani;Hoque, Md. Ehtesham Ul;Lee, Mijin;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
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    • v.34 no.4
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    • pp.1096-1100
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    • 2013
  • The kinetic studies on the reactions of O-methyl (1), O-propyl (3) and O-isopropyl (4) phenyl phosphonochloridothioates with substituted anilines and deuterated anilines have been carried out in acetonitrile at $55.0^{\circ}C$. A concerted $S_N2$ mechanism is proposed for the anilinolyses of 1, 3 and 4. The anilinolysis rates of the phosphonochloridothioates are predominantly dependent upon the steric effects over the inductive effects of the two ligands. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal with 1 and 3, while secondary inverse with 4. Primary normal and secondary inverse DKIEs are rationalized by frontside and backside nucleophilic attack transition state, respectively. The DKIEs of the phosphonochloridothioates do not have any consistent correlations with the two ligands.

Schisandrol A and gomisin N from Schisandra chinensis extract improve hypogonadism via anti-oxidative stress in TM3 Leydig cells

  • Jia Bak;Seung Ju Lee;Tae Won Kim;Seonhwa Hwang;Min Ju Park;Rohith Arunachalam;Eunsoo Yoo;Min Hi Park;Yun-Sik Choi;Hye Kyung Kim
    • Nutrition Research and Practice
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    • v.17 no.1
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    • pp.1-12
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    • 2023
  • BACKGROUND/OBJECTIVES: Male hypogonadism is a condition where the body does not produce enough testosterone and significantly impacts health. Age, obesity, genetics, and oxidative stress are some physiological factors that may contribute to testosterone deficiency. Previous studies have shown many pharmacological benefits of Schisandra chinensis (S. chinensis) Baillon as an anti-inflammatory and antioxidant. However, the molecular mechanism of attenuating hypogonadism is yet to be well established. This research was undertaken to study the effects of S. chinensis extract (SCE) on testosterone deficiency. MATERIALS/METHODS: S. chinensis fruit was pulverized and extracted using 60% aqueous ethanol. HPLC analysis was performed to analyze and quantify the lignans of the SCE. RESULTS: The 2,2-diphenyl-2-picrylhydrazyl and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) scavenging assays confirmed that the SCE and its major lignans (schisandrol A and gomisin N) inhibit oxidative stress. Effects of SCE analysis on the testosterone level under oxidative stress conditions revealed that both schisandrol A and gomisin N were able to recover the lowered testosterone levels. Through mRNA expression of TM3 Leydig cell, we observed that the SCE lignans were able to induce the enzymes involved in testosterone biosynthesis-related genes such as 3β-HSD4 (P < 0.01 for SCE, and P < 0.001 for schisandrol A and gomisin N), 17β-HSD3 (P < 0.001 for SCE, schisandrol A and gomisin N), and 17, 20-desmolase (P < 0.01 for schisandrol A, and P < 0.001 for SCE and gomisin N). CONCLUSIONS: These results support that SCE and its active components could be potential therapeutic agents for regulating and increasing testosterone production.

Characteristics of Turbulent Lifted Flames in Coflow Jet with Initial Temperature Variations (동축류 제트에서 초기 온도 변화에 따른 난류 부상화염 특성)

  • Kim, K.N.;Won, S.H.;Chung, S.H.
    • Journal of the Korean Society of Combustion
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    • v.9 no.1
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    • pp.32-38
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    • 2004
  • Characteristics of turbulent lifted flames in coflow jet have been investigated by varying initial temperature through the heating coflow air. In the turbulent regime, liftoff height increases linearly with fuel jet velocity and decreases nonlinearly as the coflow temperature increases. This can be attributed to the increase of turbulent propagation speed, which is strongly related to laminar burning velocity. Dimensionless liftoff heights are correlated well with dimensionless jet velocity, which are scaled with parameters determining local flow velocity and turbulent propagation speed. This implies that the turbulent lifted flames are stabilized by balance mechanism between local turbulent burning velocity and flow velocity. Blowout velocity can be obtained from the ratio of mixing time to chemical time. Comparing to previous researches, thermal diffusivity should be evaluated from the initial temperature instead of adiabatic flame temperature.

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DEVELOPMENT OF INNER-SPHERICAL CONTINUOUSLY VARIABLE TRANSMISSION FOR BICYCLES

  • Park, M.W.;Lee, H.W.;Park, N.G.;Sang, H.S.
    • International Journal of Automotive Technology
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    • v.8 no.5
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    • pp.593-598
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    • 2007
  • A new continuously variable transmission for bicycles(B-CVT) is developed by using a traction drive mechanism having inner and outer spherical rotors. The B-CVT has high power efficiency, large torque capacity, improved drivability and good packageability. The ratio change mechanism for the B-CVT is very simple, in contrast with other traction drive CVTs. After completing a conceptual design, a performance analysis and a detail design, a prototype of the B-CVT has been manufactured. The prototype has rated power of 100 watts, pedal speed of 6 rad/s and an overall speed ratio of 1.0-4.0. A bench test and an actual bicycle test have been performed to verify the practicability of the B-CVT.

Spectroscopic Studies on the Interaction of N-alkyl Phenothiazines with Bovine Serum Albumin

  • Seetharamappa, J.;Shaikh, S.M.T;Kamat, B.P.
    • Journal of Photoscience
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    • v.12 no.1
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    • pp.25-32
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    • 2005
  • Binding of N-Alkyl phenothiazines (NAP) to bovine serum albumin (BSA) was studied by spectroscopic methods.It was found that the phenothiazine ring common to all drugs makes major contribution to interaction. However, the nature of alkylamino group at position 10 influences the protein binding significantly. Stern-Volmer plots indicated the presence of static component in the quenching mechanism. The high magnitude of rate constant of quenching indicated that the process of energy transfer occurs by intermolecular interaction and thus the drug-binding site is in close proximity to tryptophan residues of BSA. Binding studies in presence of hydrophobic probe, 8-anilino-1-naphthalein-sulphonic acid showed that there is hydrophobic interaction between drug and the probe and they do not share common sites in BSA. Thermodynamic parameters obtained from data at different temperatures showed that the binding of NAP to BSA predominantly involve hydrophobic forces. The effects of some cations and anions common ions were investigated on NAP-BSA interactions. The CD spectrum of BSA in presence of drug showedthat binding of drug leads to change in the helicity of the protein.

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RUNX1 Upregulation Causes Mitochondrial Dysfunction via Regulating the PI3K-Akt Pathway in iPSC from Patients with Down Syndrome

  • Yanna Liu;Yuehua Zhang;Zhaorui Ren;Fanyi Zeng;Jingbin Yan
    • Molecules and Cells
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    • v.46 no.4
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    • pp.219-230
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    • 2023
  • Down syndrome (DS) is the most common autosomal aneuploidy caused by trisomy of chromosome 21. Previous studies demonstrated that DS affected mitochondrial functions, which may be associated with the abnormal development of the nervous system in patients with DS. Runt-related transcription factor 1 (RUNX1) is an encoding gene located on chromosome 21. It has been reported that RUNX1 may affect cell apoptosis via the mitochondrial pathway. The present study investigated whether RUNX1 plays a critical role in mitochondrial dysfunction in DS and explored the mechanism by which RUNX1 affects mitochondrial functions. Expression of RUNX1 was detected in induced pluripotent stem cells of patients with DS (DS-iPSCs) and normal iPSCs (N-iPSCs), and the mitochondrial functions were investigated in the current study. Subsequently, RUNX1 was overexpressed in N-iPSCs and inhibited in DS-iPSCs. The mitochondrial functions were investigated thoroughly, including reactive oxygen species levels, mitochondrial membrane potential, ATP content, and lysosomal activity. Finally, RNA-sequencing was used to explore the global expression pattern. It was observed that the expression levels of RUNX1 in DS-iPSCs were significantly higher than those in normal controls. Impaired mitochondrial functions were observed in DS-iPSCs. Of note, overexpression of RUNX1 in N-iPSCs resulted in mitochondrial dysfunction, while inhibition of RUNX1 expression could improve the mitochondrial function in DS-iPSCs. Global gene expression analysis indicated that overexpression of RUNX1 may promote the induction of apoptosis in DS-iPSCs by activating the PI3K/Akt signaling pathway. The present findings indicate that abnormal expression of RUNX1 may play a critical role in mitochondrial dysfunction in DS-iPSCs.

Nucleophilic Displacement at Sulfur Center (ⅩⅢ). Solvolysis of para-Substituted Benzenesulfonyl Chlorides in MeOH-MeCN Mixtures (황의 친핵성 치환반응 (제13보). 메탄올-아세토니트닐계에서의 파라치환 염화벤젠술포닐의 가용매 분해반응)

  • Ikchoon Lee;In Sun Koo
    • Journal of the Korean Chemical Society
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    • v.25 no.1
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    • pp.7-12
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    • 1981
  • Solvolysis of $p-CH_3, p-H, p-Cl and p-NO_2$-benzenesulfonyl chlorides have heen studied in MeOH-MeCN mixtures. A nonlinear Hammett plot with a ratio order of p-NO_2 > p-CH_3 > p-H > p-Cl was obtained; the reaction was thought to proceed by an S_N1-S_N2 borderline mechanism. In all cases the reactivity was a maximum at 90∼95%(v) methanol, whereas methanol monomer selectivity defined as fi = \frac{k1}{ki}i (k1; observed pseudo-first order rate constant: ki; hypothetical rate constant for MeOH solution having the same polymer structure as in the pure MeOH) was a maximum at 80% methanol with a decreasing order of fi as p-NO_2 > p-Cl > p-H > p-CH_3.$ This was interpreted as the decrease in tightness of transition state; the larger the fi, the tighter is the MeOH attached to the substrate, and hence the more susceptible the substrate becomes to the approaching monomer methanol.

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