• Title/Summary/Keyword: Charge resonance

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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.

Structure-Reactivity Correlations in Nucleophilic Displacement Reactions of Y-Substituted-Phenyl X-Substituted-Cinnamates with Z-Substituted-Phenoxides

  • Son, Yu-Jin;Kim, Eun-Hee;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2455-2460
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    • 2013
  • Second-order rate constants ($k_N$) have been measured spectrophotometrically for the nucleophilic displacement reactions of 4-nitrophenyl X-substituted-cinnamates (4a-4e) and Y-substituted-phenyl cinnamates (5a-5e) with Z-substituted-phenoxide anions in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 4a-4e with 4-chlorophenoxide (4-$ClPhO^-$) consists of two intersecting straight lines, which might be taken as a change in the rate-determining step (RDS). However, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of substrates possessing an electron-withdrawing group in the cinnamoyl moiety through resonance interactions, since the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}X=0.89$ and r = 0.58. The Br${\o}$nsted-type plot for the reactions of 4-nitrophenyl cinnamate (4c) with Z-substituted-phenoxides is linear with ${\beta}_{nuc}=0.76$. The Br${\o}$nsted-type plot for the reactions of Y-substituted-phenyl cinnamates (5a-5d) with 4-chlorophenoxides (4-$ClPhO^-$) is also linear with ${\beta}_{lg}=-0.72$. The Hammett plot correlated with ${\sigma}^-$ constants for the reactions of 5a-5d results in a much better linear correlation than that correlated with ${\sigma}^o$ constants, indicating that a partial negative charge develops on the O atom of the leaving aryloxide. Thus, the reactions have been concluded to proceed through a concerted mechanism.

Improvement in the bias stability of zinc oxide thin-film transistors using an $O_2$ plasma-treated silicon nitride insulator

  • Kim, Ung-Seon;Mun, Yeon-Geon;Gwon, Tae-Seok;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.180-180
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    • 2010
  • Thin film transistors (TFTs) based on oxide semiconductors have emerged as a promising technology, particularly for active-matrix TFT-based backplanes. Currently, an amorphous oxide semiconductor, such as InGaZnO, has been adopted as the channel layer due to its higher electron mobility. However, accurate and repeatable control of this complex material in mass production is not easy. Therefore, simpler polycrystalline materials, such as ZnO and $SnO_2$, remain possible candidates as the channel layer. Inparticular, ZnO-based TFTs have attracted considerable attention, because of their superior properties that include wide bandgap (3.37eV), transparency, and high field effect mobility when compared with conventional amorphous silicon and polycrystalline silicon TFTs. There are some technical challenges to overcome to achieve manufacturability of ZnO-based TFTs. One of the problems, the stability of ZnO-based TFTs, is as yet unsolved since ZnO-based TFTs usually contain defects in the ZnO channel layer and deep level defects in the channel/dielectric interface that cause problems in device operation. The quality of the interface between the channel and dielectric plays a crucial role in transistor performance, and several insulators have been reported that reduce the number of defects in the channel and the interfacial charge trap defects. Additionally, ZnO TFTs using a high quality interface fabricated by a two step atomic layer deposition (ALD) process showed improvement in device performance In this study, we report the fabrication of high performance ZnO TFTs with a $Si_3N_4$ gate insulator treated using plasma. The interface treatment using electron cyclotron resonance (ECR) $O_2$ plasma improves the interface quality by lowering the interface trap density. This process can be easily adapted for industrial applications because the device structure and fabrication process in this paper are compatible with those of a-Si TFTs.

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Improved Current Source Design to Measure Induced Magnetic Flux Density Distributions in MREIT

  • Oh Tong-In;Cho Young;Hwang Yeon-Kyung;Oh Suk-Hoon;Woo Eung-Je;Lee Soo-Yeol
    • Journal of Biomedical Engineering Research
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    • v.27 no.1
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    • pp.30-37
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    • 2006
  • Injecting currents into an electrically conducting subject, we may measure the induced magnetic flux density distributions using an MRI scanner. The measured data are utilized to reconstruct cross-sectional images of internal conductivity and current density distributions in Magnetic Resonance Electrical Impedance Tomography (MREIT). Injection currents are usually provided in a form of mono-polar or bi-polar pulses synchronized with an MR pulse sequence. Given an MRI scanner performing the MR phase imaging to extract the induced magnetic flux density data, the current source becomes one of the key parts determining the signal-to-noise ratio (SNR) of the measured data. Since this SNR is crucial in determining the quality of reconstructed MREIT images, special care must be given in the design and implementation of the current source. This paper describes a current source design for MREIT with features including interleaved current injection, arbitrary current waveform, electrode switching to discharge any stored charge from previous current injections, optical isolation from an MR spectrometer and PC, precise current injection timing control synchronized with any MR pulse sequence, and versatile PC control program. The performance of the current source was verified using a 3T MRI scanner and saline phantoms.

Effect of additives on the hydrothermal synthesis of manganese ferrite nanoparticles

  • Kurtinaitiene, Marija;Mazeika, Kestutis;Ramanavicius, Simonas;Pakstas, Vidas;Jagminas, Arunas
    • Advances in nano research
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    • v.4 no.1
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    • pp.1-14
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    • 2016
  • Superparamagnetic iron oxide nanoparticles (Nps), composed of magnetite, $Fe_3O_4$, or maghemite, ${\gamma}-Fe_2O_3$, core and biocompatible polymer shell, such as dextran or chitozan, have recently found wide applications in magnetic resonance imaging, contrast enhancement and hyperthermia therapy. For different diagnostic and therapeutic applications, current attempt is focusing on the synthesis and biomedical applications of various ferrite Nps, such as $CoFe_2O_4$ and $MnFe_2O_4$, differing from iron oxide Nps in charge, surface chemistry and magnetic properties. This study is focused on the synthesis of manganese ferrite, $MnFe_2O_4$, Nps by most commonly used chemical way pursuing better control of their size, purity and magnetic properties. Co-precipitation syntheses were performed using aqueous alkaline solutions of Mn(II) and Fe(III) salts and NaOH within a wide pH range using various hydrothermal treatment regimes. Different additives, such as citric acid, cysteine, glicine, polyetylene glycol, triethanolamine, chitosan, etc., were tested on purpose to obtain good yield of pure phase and monodispersed Nps with average size of ${\leq}20nm$. Transmission electron microscopy (TEM), X-ray diffraction, energy dispersive X-ray spectroscopy (EDX), $M\ddot{o}ssbauer$ spectroscopy down to cryogenic temperatures, magnetic measurements and inductively coupled plasma mass spectrometry were employed in this study.

Preparation of Bi/Bi2MoO6 Plasmonic Photocatalyst with High Photocatalytic Activity Under Visible Light Irradiation

  • Zou, Chentao;Yang, Zhiyuan;Liang, Mengjun;He, Yunpeng;Yang, Yun;Yang, Shuijin
    • Nano
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    • v.13 no.11
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    • pp.1850127.1-1850127.13
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    • 2018
  • Bi metal deposited on $Bi_2MoO_6$ composite photocatalysts have been successfully synthesized via a simple reduction method at room temperature with using $NaBH_4$ as the reducing agent. The photocatalytic activity of the composite was evaluated by degradation of rhodamine B (RhB) and bisphenol A (BPA) solution under visible light. The rate constant of $Bi/Bi_2MoO_6$ composite to RhB is 10.8 times that of $Bi_2MoO_6$, and the degradation rate constant of BPA is 6.9 times of that of $Bi_2MoO_6$. Nitrogen absorption-desorption isotherm proved that the increase of specific surface area is one of the reasons for the improvement of photocatalytic degradation activity of $Bi/Bi_2MoO_6$ composites. The higher charge transfer efficiency of $Bi/Bi_2MoO_6$ is found through the characterization of the photocurrent and impedance, which are attributed to the surface plasmon resonance (SPR) effect produced by the introduction of the metal Bi monomer in the composite. Free radical capture experiments proved that cavitation is the main active species. Based on the above conclusions, a possible mechanism of photocatalytic degradation is proposed.

A Study on the Setting of Examination Limits for Radiographers in Medical Institutions (의료기관 내 방사선사의 검사 한도 설정에 관한 연구)

  • Jeong-Ho Kim;Gap-Jung Kim
    • Journal of the Korean Society of Radiology
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    • v.17 no.3
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    • pp.401-410
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    • 2023
  • A radiographer is a job in charge of diagnostic imaging equipment, and must contribute to the promotion of public health by suggesting an appropriate level of work. To this end, we intend to present an appropriate level of work through evaluation of human harm according to work, statistical evaluation through questionnaires, and domestic and international trends. In the case of human harm evaluation, considering radiation exposure, 42.6%, shield work, 69.7%, and in the case of magnetic resonance imaging, the maximum length of stay in the examination room should be adjusted to 15 minutes and not exceed 30 times. According to the survey statistics, it was confirmed that the physical and mental burden increased due to the high workload and difficulty compared to working hours. Based on domestic and international trends, it is necessary to adjust the examination standards for domestic radiographers to 36.8% to promote national health through qualitative improvement of radiological examinations. something to do.

Production of Mono-Hydroxylated Derivatives of Terpinen-4-ol by Bacterial CYP102A1 Enzymes

  • Jeong-Hoon Kim;Chan Mi Park;Hae Chan Jeong;Gyeong Han Jeong;Gun Su Cha;Sungbeom Lee;Chul-Ho Yun
    • Journal of Microbiology and Biotechnology
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    • v.34 no.3
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    • pp.725-734
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    • 2024
  • CYP102A1 from Bacillus megaterium is an important enzyme in biotechnology, because engineered CYP102A1 enzymes can react with diverse substrates and produce human cytochrome P450-like metabolites. Therefore, CYP102A1 can be applied to drug metabolite production. Terpinen-4-ol is a cyclic monoterpene and the primary component of essential tea tree oil. Terpinen-4-ol was known for therapeutic effects, including antibacterial, antifungal, antiviral, and anti-inflammatory. Because terpenes are natural compounds, examining novel terpenes and investigating the therapeutic effects of terpenes represent responses to social demands for eco-friendly compounds. In this study, we investigated the catalytic activity of engineered CYP102A1 on terpinen-4-ol. Among CYP102A1 mutants tested here, the R47L/F81I/F87V/E143G/L188Q/N213S/E267V mutant showed the highest activity to terpinen-4-ol. Two major metabolites of terpinen-4-ol were generated by engineered CYP102A1. Characterization of major metabolites was confirmed by liquid chromatography-mass spectrometry (LC-MS), gas chromatography-MS, and nuclear magnetic resonance spectroscopy (NMR). Based on the LC-MS results, the difference in mass-to-charge ratio of an ion (m/z) between terpinen-4-ol and its major metabolites was 16. One major metabolite was defined as 1,4-dihydroxyp-menth-2-ene by NMR. Given these results, we speculate that another major metabolite is also a mono-hydroxylated product. Taken together, we suggest that CYP102A1 can be applied to make novel terpene derivatives.

Influence of substituted phenylcarbamoyl group on the fungicidal activites of a new 5,6-dihydro-2-trifluoromethyl-1,4-oxathiincarboxanilide derivatives (새로운 5,6-dihydro-2-trifluoromethyl-1,4-oxathiincarboxanilide 유도체의 항균활성에 미치는 치환-phenylcarbamoyl group의 영향)

  • Sung, Nack-Do;Yu, Seong-Jae;Nam, Kee-Dal;Chang, Kee-Hyuk;Hahn, Hoh-Gyu
    • The Korean Journal of Pesticide Science
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    • v.2 no.3
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    • pp.64-69
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    • 1998
  • New thirty derivatives of 5,6-dihydro-2-trifluoromethyl-1,4-oxathiin carboxanilide as substrate(S) were synthesized and their fungicidal activities in vivo against rice sheath blight(Rhizoctonia solani) and wheat leaf rust(Puccinia recondita) were examined. The structure activity relationships(SAR) between the activities($pI_{50}$) and a physicochemical parameters of substituents(X) at the phenylcarbamoyl group were analyzed using the adaptive regression analysis method. The 3-methoxy, 11, 3-isopropyloxy, 13 and 3-isopropyl substituent, 25 as X on the phenylcarbamoyl group exhibited the most highest fungicidal activity against the two fungi. The fungicidal potency of the (S) against Puccinia recondita was higher than Rhizoctonia solani. In case of Rhizoctonia solani, the molecular hydrophobicity(${\pi}>0$) and resonance effect(R<0) by meta-alkyl substitutents with electron donating were important factors in determining fungicidal activity. And the HOMO energy(HOMO>0), ABSQ, sum of absolute values of the atomic charges on each atom and specific polarizability(Sp.Pol<0) of (S) were significantly influential towards fungicidal activity against Puccinia recondita.. The interaction between (S) and receptor agonist from the based on SAR studies proceeds through charge-control reaction, and conditions to show higher activity has been also discussed.

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Optical Properties of Oxotitanium (Ⅳ) Meso-tetrakis(4-sulfonatophenyl)porphyrin Intercalated into the Layered Double Hydroxides (LDH) Studied by Laser Spectroscopy

  • Ryu, Su-Young;Yoon, Min-Joong;Choy, Jin-Ho;Hwang, Sung-Ho;Frube, Akihiro;Asahi, Tsuyoshi;Hiroshi, Masuhara
    • Bulletin of the Korean Chemical Society
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    • v.24 no.4
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    • pp.446-452
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    • 2003
  • Some new nanohybrid materials have been synthesized by intercalating the oxotitanium(IV) meso-tetrakis(4- sulfonatophenyl) porphyrin$(O=Ti^{(IV)} TSPP)$ into the Zn/Al layered double hydroxides (LDHs), and their structures and photophysical properties have been investigated by various laser spectroscopic techniques. According to the XRD pattern of the synthesized nanohybrid materials, the macrocycle plane of $O=Ti^{(IV)}$ TSPP are grafted perpendicular to the LDH layers. The $O=Ti^{(IV)}$ TSPP-intercalated LDH exhibits band broadening of the absorption spectrum and a blue shift of Q-band as compared to that observed in solution. Resonance Raman spectral measurements demonstrate that the positively charged LDHs give rise to a slight decrease of the electronic density of the porphyrin ring accompanying a small change of the electronic distribution of the $O=Ti^{(IV)}$ TSPP. Consequently the LDH environment affects the energies of the two highest occupied molecular orbitals (HOMOs) of the $O=Ti^{(IV)}$) TSPP, $a_{1u}$ and $a_{2u}$, producing a mixed orbital character. Being consistent with these electronic structural changes of $O=Ti^{(IV)}$ TSPP in LDH, both the fluorescence spectral change and the fsdiffuse reflectance transient measurements imply that the photoexcitation of the $O=Ti^{(IV)}$ TSPP intercalated into LDH undergoes fast relaxation to the O=Ti(IV) $TSPP^+-LDH^- $charge transfer (CT) state within a few picoseconds, followed by a photoinduced electron transfer between the O=Ti(IV) TSPP and LDHs with a rate constant greater than %1×10^{10}S^{-1}$. No evidence is found for back electron transfer. In conclusion, the $O=Ti^{(IV)}$ TSPP intercalated LDH seems to be a possible candidate for an artificial reaction center for an efficient solar energy conversion system.