• Title/Summary/Keyword: reactive type

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The α-Effect in Nucleophilic Substitution Reactions of Y-Substituted-Phenyl Diphenylphosphinates with HOO- and OH-

  • Hong, Hyo-Jeong;Bae, Ae Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2251-2255
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    • 2013
  • Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

Overexpression of Heat Shock Factor Gene HsfA3 Increases Galactinol Levels and Oxidative Stress Tolerance in Arabidopsis

  • Song, Chieun;Chung, Woo Sik;Lim, Chae Oh
    • Molecules and Cells
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    • v.39 no.6
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    • pp.477-483
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    • 2016
  • Heat shock factors (Hsfs) are central regulators of abiotic stress responses, especially heat stress responses, in plants. In the current study, we characterized the activity of the Hsf gene HsfA3 in Arabidopsis under oxidative stress conditions. HsfA3 transcription in seedlings was induced by reactive oxygen species (ROS), exogenous hydrogen peroxide ($H_2O_2$), and an endogenous $H_2O_2$ propagator, 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB). HsfA3-overexpressing transgenic plants exhibited increased oxidative stress tolerance compared to untransformed wild-type plants (WT), as revealed by changes in fresh weight, chlorophyll fluorescence, and ion leakage under light conditions. The expression of several genes encoding galactinol synthase (GolS), a key enzyme in the biosynthesis of raffinose family oligosaccharides (RFOs), which function as antioxidants in plant cells, was induced in HsfA3 overexpressors. In addition, galactinol levels were higher in HsfA3 overexpressors than in WT under unstressed conditions. In transient transactivation assays using Arabidopsis leaf protoplasts, HsfA3 activated the transcription of a reporter gene driven by the GolS1 or GolS2 promoter. Electrophoretic mobility shift assays showed that GolS1 and GolS2 are directly regulated by HsfA3. Taken together, these findings provide evidence that GolS1 and GolS2 are directly regulated by HsfA3 and that GolS enzymes play an important role in improving oxidative stress tolerance by increasing galactinol biosynthesis in Arabidopsis.

Optimal Remediation of TCE-contaminated Groundwater using Direct Current and Fe$^0$ (직류전원과 0가 철을 이용한 지하수내 TCE정화효율의 최적화 연구)

  • Moon, Ji-Won;Moon, Hi-Soo;Roh, Yul;Kim, Heon-Ki;Song, Yun-Goo
    • Economic and Environmental Geology
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    • v.35 no.3
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    • pp.229-239
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    • 2002
  • The objective of this study was to design an optimal electro-remediation system for TCE contaminated water using zero talent iron (ZVI) and direct current (DC). A series of column experiments were conducted to evaluate the effects of electrode arrangement and the location of permeable iron barrier in the column on the TCE removal efficiency and iron corrosion process. In twelve different combinations of ZVI and/or DC application in the test columns, the rate of reductive degradation of TCE was improved with simultaneous application of both ZVI and DC compared to that used ZVI only. The moot effective arrangement of electrode and ZVI for TCE removal from water was a column set with ZVI and cathode installed at the down gradient, respectively.

Cilostazol ameliorates diabetic nephropathy by inhibiting high-glucose-induced apoptosis

  • Chian, Chien-Wen;Lee, Yung-Shu;Lee, Yi-Ju;Chen, Ya-Hui;Wang, Chi-Ping;Lee, Wen-Chin;Lee, Huei-Jane
    • The Korean Journal of Physiology and Pharmacology
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    • v.24 no.5
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    • pp.403-412
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    • 2020
  • Diabetic nephropathy (DN) is a hyperglycemia-induced progressive development of renal insufficiency. Excessive glucose can increase mitochondrial reactive oxygen species (ROS) and induce cell damage, causing mitochondrial dysfunction. Our previous study indicated that cilostazol (CTZ) can reduce ROS levels and decelerate DN progression in streptozotocin (STZ)-induced type 1 diabetes. This study investigated the potential mechanisms of CTZ in rats with DN and in high glucose-treated mesangial cells. Male Sprague-Dawley rats were fed 5 mg/kg/day of CTZ after developing STZ-induced diabetes mellitus. Electron microscopy revealed that CTZ reduced the thickness of the glomerular basement membrane and improved mitochondrial morphology in mesangial cells of diabetic kidney. CTZ treatment reduced excessive kidney mitochondrial DNA copy numbers induced by hyperglycemia and interacted with the intrinsic pathway for regulating cell apoptosis as an antiapoptotic mechanism. In high-glucose-treated mesangial cells, CTZ reduced ROS production, altered the apoptotic status, and down-regulated transforming growth factor beta (TGF-β) and nuclear factor kappa light chain enhancer of activated B cells (NF-κB). Base on the results of our previous and current studies, CTZ deceleration of hyperglycemia-induced DN is attributable to ROS reduction and thereby maintenance of the mitochondrial function and reduction in TGF-β and NF-κB levels.

Compensation of Unbalanced PCC Voltage in Off-shore Wind Farms of PMSG Type Turbine

  • Kang, Jayoon;Han, Daesu;Suh, Yongsug;Jung, Byoungchang;Kim, Jeongjoong;Park, Jonghyung;Choi, Youngjoon
    • Proceedings of the KIPE Conference
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    • 2014.07a
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    • pp.215-216
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    • 2014
  • This paper proposes a control algorithm for permanent magnet synchronous generator with a back-to-back three-level neutral-point clamped voltage source converter in a medium-voltage offshore wind power system under unbalanced grid conditions. The proposed control algorithm particularly compensates for the unbalanced grid voltage at the point of common coupling in a collector bus of offshore wind power system. This control algorithm has been formulated based on the symmetrical components in positive and negative rotating synchronous reference frames under generalized unbalanced operating conditions. Instantaneous active and reactive power are described in terms of symmetrical components of measured grid input voltages and currents. Negative sequential component of ac input current is injected to the point of common coupling in the proposed control strategy. The amplitude of negative sequential component is calculated to minimize the negative sequential component of grid voltage under the limitation of current capability in a voltage source converter. The proposed control algorithm makes it possible to provide a balanced voltage at the point of common coupling resulting in the generated power of high quality from offshore wind power system under unbalanced network conditions.

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Relationship of the Signal Transduction-mediated Proteins and Enzymes to Contractility and Plasticity in Skeletal Muscles (골격근의 수축과 가소성에 대한 신호전달-매개 단백질 및 관련 효소의 상관성)

  • Kim, Jung-Hwan
    • The Journal of Korean Physical Therapy
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    • v.19 no.4
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    • pp.1-14
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    • 2007
  • Background: It is generally accepted that skeletal muscle contraction is triggered by nerve impulse and intracellular $Ca^{2+}\;([Ca^{2+}]_i)$ released from intracellular $Ca^{2+}$ stores such as sarcoplasmic reticulum (SR). Specifically, this process, called excitation-contraction (E-C) coupling, takes place at intracellular junctions between the plasma membrane, the transverse (T) tubule L-type $Ca^{2+}$ channel (dihydropyridine-sensitive L-rype $Ca^{2+}$ channel, DHPR, also called tetrads), and the SR $Ca^{2+}$ release channel (ryanodine-sensitive $Ca^{2+}$ release channel, RyR, also called feet) of internal $Ca^{2+}$ stores in skeletal muscle cells. Furthermore, it has been reported that the $Ca^{2+-}$ dependent and -independent contraction determine the expression of skeletal muscle genes, thus providing a mechanism for tightly coupling the extent of muscle contraction to regulation of muscle plasticity-related excitation-transcription (E-T) coupling. Purpose: Expression and activity of plasticity-associated enzymes in gastrocnemius muscle strips have not been well studied, however. Methods: Therefore, in this study the expression and phosphorylation of E-C and E-T coupling-related mediators such as protein kinases, ROS(reactive oxygen species)- and apoptosis-related substances, and others in gastrocnemius muscles from rats was examined. Results: I found that expression and activity of MAPKs (mitogen-activated protein kinases, ERK1/2, p38MAPK, and SAPK/JNK), apoptotic proteins (cleaved caspase-3, cytochrome c, Ref-1, Bad), small GTP-binding proteins (RhoA and Cdc42), actin-binding protein (cofilin), PKC (protein kinase C) and $Ca^{2+}$ channel (transient receptor potential channel 6, TRPC6) was observed in rat gastrocnemius muscle strips. Conclusion: These results suggest that MAPKs, ROS- and apoptosis-related enzymes, cytoskeleton-regulated proteins, and $Ca^{2+}$ channel may in part functionally import in E-C and E-T coupling from rat skeletal muscles.

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The improvement of Cu metal film adhesion on polymer substrate by the low-power High-frequency ion thruster

  • Jung Cho;Elena Kralkina;Yoon, Ki-Hyun;Koh, Seok-Keun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2000.02a
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    • pp.60-60
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    • 2000
  • The adhesion interface formation between copper and poly(ethylene terephthalate)(PET), poly(methyl methacrylate)(PMMA) and Polyimide films was treated using Ion assisted reaction system to sequential sputter deposition by High-Frequency ion source. The ion beam modification system used a new type of low power HF ion thruster for space application as new low thruster electric propulsion system. Low power HF ion thruster with diameter 100mm gives the opportunity to obtain beams of Ar+ with currents 20~150 mA (current density 0.5~3.5 mA/cm2) and energy 200~2500eV at HF power level 10~150 W. Using Ar as a working gas it is possible to obtain thrust within 3~8 mN. Contact angles for untreated films were over 95$^{\circ}$ and 80 for Pet, 10o for PMMA and 12o for PI samples as a condition of ion assisted reaction at the ion dose of 10$\times$1016 ions/cm2, the ion beam potential of 1.2 keV and 4 ml/min for environmental gas flow rate. 900o peel tests yielded values of 15 to 35 for PET, 18 to 40 and 12 to 36 g/min. respectively. High resolution X-ray photoelectron spectrocopy is the Cls region for Cu metal on these polymer substrates showed increases in C=O-O groups for polymide, whereas PET and PMMA treated samples showed only C=O groups with increase the ion dose. Finally, unstable polymer surface can be changed from hydrophobic to hydrophilic formation such as C-O and C=O that were confirmed by the XPS analysis, conclusionally, the ion assisted reaction is very effective tools to attach reactive ion species to form functional groups on C-C bond chains of PET, PMMA and PI.

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Development of one batch type and multi functional agent for CPB process (CPB용 다기능성 일욕형 조제 개발)

  • Park, Beob;Cho, Yeon-Jeong;Koo, Kang
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2011.11a
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    • pp.32-32
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    • 2011
  • Cold Pad batch(CPB)처리에 의한 직물 전처리 공정은 특히 저온처리방식이라 에너지 소모가 적으며, 발생되는 대기오염 및 용수사용량이 연속식 방법에 비해 약 30%이상 절감되는 경제적 친환경적인 기술로 특히 정련과 표백을 동시에 수행할 수 있다. CPB 전처리는 호발, 정련, 표백을 포함하는 공정으로 일욕으로 처리시 패딩, 수세, 와인딩 공정을 단축시키기 때문에 약품 소비량 감소와 에너지 사용 절감 효과가 있어 전 세계적으로 확산되고 있는 Green Technology이다. 본 연구에서는 CPB용 다기능성 일욕형 조제에 개발하기 위해 전처리시 정련, 표백성에 대한 연구를 진행하였다. 시료는 NP/C 교직물을 사용하였고, CPB 처리액은 원료 및 첨가용제를 여러 비율로 조합하여 조제를 formulation 하였다. 이를 사용하여 패딩, 배칭, 수세 및 건조하여 전처리를 하였다. 표백된 정도를 파악하기 위해 Macbeth Color Eye-3100을 사용하여 백도(whiteness(CIE))를 5회 평균값을 구하여 측정 하였다. 정련된 정도를 비교하기 위해 C.I.Reactive Red 238의 2g/l 용액을 사용하여 wicking test를 하였다. 1분간 흡수높이를 측정하여 정련성을 확인하였다. 각각의 첨가용제를 비교한 결과 isopropyl alcohol을 첨가 시 hexylene glycol, butyl diglycol를 첨가한 경우에 비해 높은 흡수높이를 나타내었다. isopropyl alcohol의 농도별 정련성을 알아보기 위해 0%, 5%, 10%의 농도로 처리하였다. 그 결과 isopropyl alcohol 첨가량이 많을수록 정련성이 증가하였다. 다기능성 일욕조제의 문제점인 알칼리 안정성 부족을 보완하기 위해 polyoxyethlylene tridecyl ether derivatieves(LAP300)의 인화물을 첨가하였다. LAP300의 첨가량이 증가할수록 정련성이 증가하는 경향을 나타내었다. 알칼리 안정성 및 타 성능(정련성, 백도, 킬레이트 성)을 종합적으로 평가하여 향후, CPB용 다기능성 일욕형 조제의 개발에 대한 연구를 진행할 계획이다.

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Influence of vacancy defects on vibration analysis of graphene sheets applying isogeometric method: Molecular and continuum approaches

  • Tahouneh, Vahid;Naei, Mohammad Hasan;Mashhadi, Mahmoud Mosavi
    • Steel and Composite Structures
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    • v.34 no.2
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    • pp.261-277
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    • 2020
  • The main objective of this research paper is to consider vibration analysis of vacancy defected graphene sheet as a nonisotropic structure via molecular dynamic and continuum approaches. The influence of structural defects on the vibration of graphene sheets is considered by applying the mechanical properties of defected graphene sheets. Molecular dynamic simulations have been performed to estimate the mechanical properties of graphene as a nonisotropic structure with single- and double- vacancy defects using open source well-known software i.e., large-scale atomic/molecular massively parallel simulator (LAMMPS). The interactions between the carbon atoms are modelled using Adaptive Intermolecular Reactive Empirical Bond Order (AIREBO) potential. An isogeometric analysis (IGA) based upon non-uniform rational B-spline (NURBS) is employed for approximation of single-layered graphene sheets deflection field and the governing equations are derived using nonlocal elasticity theory. The dependence of small-scale effects, chirality and different defect types on vibrational characteristic of graphene sheets is investigated in this comprehensive research work. In addition, numerical results are validated and compared with those achieved using other analysis, where an excellent agreement is found. The interesting results indicate that increasing the number of missing atoms can lead to decrease the natural frequencies of graphene sheets. It is seen that the degree of the detrimental effects differ with defect type. The Young's and shear modulus of the graphene with SV defects are much smaller than graphene with DV defects. It is also observed that Single Vacancy (SV) clusters cause more reduction in the natural frequencies of SLGS than Double Vacancy (DV) clusters. The effectiveness and the accuracy of the present IGA approach have been demonstrated and it is shown that the IGA is efficient, robust and accurate in terms of nanoplate problems.

TGF-β downregulation-induced cancer cell death is finely regulated by the SAPK signaling cascade

  • Han, Zhezhu;Kang, Dongxu;Joo, Yeonsoo;Lee, Jihyun;Oh, Geun-Hyeok;Choi, Soojin;Ko, Suwan;Je, Suyeon;Choi, Hye Jin;Song, Jae J.
    • Experimental and Molecular Medicine
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    • v.50 no.12
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    • pp.4.1-4.19
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    • 2018
  • Transforming growth factor $(TGF)-{\beta}$ signaling is increasingly recognized as a key driver in cancer. In progressive cancer tissues, $TGF-{\beta}$ promotes tumor formation, and its increased expression often correlates with cancer malignancy. In this study, we utilized adenoviruses expressing short hairpin RNAs against $TGF-{\beta}1$ and $TGF-{\beta}2$ to investigate the role of $TGF-{\beta}$ downregulation in cancer cell death. We found that the downregulation of $TGF-{\beta}$ increased the phosphorylation of several SAPKs, such as p38 and JNK. Moreover, reactive oxygen species (ROS) production was also increased by $TGF-{\beta}$ downregulation, which triggered Akt inactivation and NOX4 increase-derived ROS in a cancer cell-type-specific manner. We also revealed the possibility of substantial gene fluctuation in response to $TGF-{\beta}$ downregulation related to SAPKs. The expression levels of Trx and GSTM1, which encode inhibitory proteins that bind to ASK1, were reduced, likely a result of the altered translocation of Smad complex proteins rather than from ROS production. Instead, both ROS and ROS-mediated ER stress were responsible for the decrease in interactions between ASK1 and Trx or GSTM1. Through these pathways, ASK1 was activated and induced cytotoxic tumor cell death via p38/JNK activation and (or) induction of ER stress.