• Title/Summary/Keyword: ${\pi}$전자-상호작용

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The Importance of $\pi$-Nonbonded Secondary Orbital Interaction on the Stereoselectivity in the (4+2) Cycloaddition Reactions of Allene Compounds (알렌화합물의 (4+2) 고리화반응에서 입체 선택성에 대한 $\pi$-비결합 2차 궤도함수 상호작용의 중요성)

  • Ikchoon Lee;Keun Bae Rhyu;Byung Choon Lee
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.133-142
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    • 1987
  • Stereoselectivities of (4+2) cycloaddition reactions of cyclopentadiene with the methyl-substituted allenic acids and esters were investigated by application of $\pi$-nonbonded interaction ($\pi$-NBI) theory. 2-FMO method has been found to be adequate for determination of endo selectivities of diene(LUMO)-dienophile (LUMO) interaction in the thermal reactions and diene (HOMO)-dienophile (LUMO) interaction in the Lewis acid catalyzed reactions. $\pi$-isoconjugate diene structure was formed by through-bond interaction of allene moiety with methyl group in the cumulated diene system; the methyl substituent acts as a conjugative chain and causes inter-level narrowing effect of the FMO's. In dienophiles which do not form $\pi$-isoconjugate diene system, methyl group acts merely as an electron donating group. In thermal reactions, the stereoselectivities are controlled by $\pi$-nonbonded secondary orbital interaction ($\pi$-NSOI) of methyl substituent, which behaves similarly as an ethylene molecule.

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MO Studies of Configuration and Conformation (XV). Through-Space and Through-Bond Interactions In Ethylene Diamine (배치와 형태에 관한 분자궤도론적 연구 (제15보). 에틸렌 디아민의 Through-Space 및 Through-Bond 상호작용)

  • Ikchoon Lee;Chang Kook Sohn;Chang Hyun Song
    • Journal of the Korean Chemical Society
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    • v.26 no.2
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    • pp.65-72
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    • 1982
  • STO-3G level computations were performed on n-propylamine, n-propylamine radical and cis-and trans-ethylene diamines in order to investigate structural contributions of (n${\pi}$/m) and (n-${\sigma}^*$) structures to the energy variations accompanying the conformational changes. It was found that (5${\pi}$/5) and (4${\pi}$/4) structures had attractive and repulsive nonbonded interactions, respectively, which were approximately additive. anti(n-${\sigma}^*$) structures had more stabilzing hyperconjugative interactions than syn(n-${\sigma}^*$) structures, but due to the large internuclear repulsion the net effect was destabilizing inthe former in contrast with the net stabilizing contribution in the latter. Moreover it was found that the stabilizing ${\pi}$-nonbond structure, (5${\pi}$/5) was always cooperatively reinforced by the more stabilizing anti(n-${\sigma}^*$) interaction, whereas the destabilizing (4${\pi}$/4) structure was accompanied by the less stabilizing syn(n-${\sigma}^*$) interaction. This type of cooperativity was found general through-bond interaction of the terminal lone pair lobes split the energy levels into two, $n_+ = \frac{1}{\sqrt{2}}(n_1 + n_2)$ and $n_- = \frac{1}{\sqrt{2}}(n_1 - n_2)$, the latter being the lower level, which can be shown using simple overlap patterns of the two lobes with a common vicinal ${\sigma}^*$ orbital.

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Effects of Ion Specificity on the Expansion Behavior of Polymer Gel with Phenyl Ring (Phenyl 고리를 갖는 고분자 겔의 팽윤거동에 대한 이온 특성화 효과)

  • Ahn, Beom-Shu
    • Journal of the Korean Applied Science and Technology
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    • v.29 no.2
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    • pp.278-285
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    • 2012
  • Effects of ion species on the expansion behavior of Poly(styrene sufonic acid)(PSSA) hydrogel were investigated in aqueous solution of selected anions, cations and hydrophobic ions. The deexpansion extent of Poly(stylene sulfonic acid) gel follow the sequence $SCN^-$<$Br^-$<$Cl^-$<$F^-$ in low concentration solutions due to the destabilization of anions to hydrogen bond between ${SO_3}^-$ and water. The deexpansion in cations followed the sequence of counterion interactions between ${SO_3}^-$ and cations. It was discussed the effects of ions on the hydrogen bonding through ${SO_3}^-$ and phenyl ring in salt solutions. Other interactions, such as the cation-${\pi}$ interaction, hydrophobic interaction, and dispersion force, contributed to the ion specific swelling of PSSA hydrogel.

Determination of Reactivities by Molecular Orbital Theory (VII). SCF-IMO Studies on the Diels-Alder Reactions between Cyclopentadiene and 2-Substituted Acrylonitriles (화학반응성의 분자궤도론적 연구 (제7보). 시클로펜타디엔과 아크릴로니트릴 치환체간의 Diels-Alder 반응에 대한 SCF-IMO 연구)

  • Lee Ikchoon;Choi Eun Wha
    • Journal of the Korean Chemical Society
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    • v.19 no.4
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    • pp.218-224
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    • 1975
  • The ground state SCF IMO theory was applied to the Diels-Alder reactions of cyclopentadiene with 2-substituted acrylonitriles. The CNDO/2 MO of the separate systems, including both $\sigma$ and $\pi$ electrons, was used as starting point. The qualitative prediction of the relative reactivity was made with the calculated primary interaction energies. Here the calculated activation energies appeared to be realistic. The stereoselectivity determined by the calculated secondary interaction energies represented the endo-selectivity for all the substituents. The reason for the slightly unsymmetrical ring closure at the transition state was discussed in terms of valence inactive electron densities of the reacting atoms.

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Development of Smart Mirror System based on the Raspberry Pi (Raspberry Pi를 이용한 스마트 미러 개발)

  • Lin, Zhi-Ming;Kim, Chul-Won
    • The Journal of the Korea institute of electronic communication sciences
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    • v.16 no.2
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    • pp.379-384
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    • 2021
  • With people's continuous research and exploration in the field of artificial intelligence, more relatively mature artificial intelligence technology is applied in people's daily life. Mirrors are the most commonly used daily necessities in life, and it should be applied to artificial intelligence. The research results of this paper show that the smart mirror designed based on the raspberry pi displays weather, temperature, greetings, and has a human-mirror interaction function. The research method of this paper uses the Raspberry pi 3B + as the core controller and Google Assistant as the intelligent control. When connected to the network via Raspberry Pi's own WiFi, the mirror can automatically display and update time, weather and news information features. You can wake up the Google Assistant using keywords, then control the mirror to play music, remind the time, It implements the function of smart mirror voice interaction. Also, all the hardware used in this study is modular assembly. Later, it is convenient for user to assemble by himself later. It is suitable for market promotion at an affordable price.

Theoretical Study of the Conformation of Cis Carbene-Olefin Transition Matal Complexes (시스 카벤-올레핀 전이금속 착물들의 형태에 대한 이론적 연구)

  • Seong-Kyu Park;Ill-Doo Kim;Joon-Tae Kim;Chang-Jin Choi;Young-Gu Cheun
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.802-811
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    • 1992
  • The conformations of several carbene-olefin-transition metal complexes[$(CO)_4M$-(CHX)olefin] (X: $OCH_3,\;NHCH_3,\;SCH_3$, M: C, Mo, W) have been studied by means of Extend Huckel calculations. In the case of $d^6$ transition metal octahedral complexes, it is shown that the two main factors which determine the optimal conformation are metal-to-ligand back-donation and direct ligand-ligand interaction at the metal, but the ligand-ligand interaction dominates the situation for a metal that is coordinated to $\pi$ acceptor ligands and to $\pi$ donor group on the carbene. The relative amounts of both factors depend strongly on the electronic nature of the ligands at the metal. The greater electron donating ability of nitrogen stabilizes amino-substituted carbene complexes compared with their alkoxyl substituted analogues. This interaction is optimal when the $\pi$ systems of the carbene and olefin are coplanar. The introduction of the $\pi$ donor group on the carbene carbon increases also the importance of the ligand-ligand interaction.

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Miscibility and Specific Intermolecular Interaction Strength of PBI/PI Blends Depending on Polyimide Structure(II) - Blend Systems with PIs Synthesized by DSDA - (폴리이미드 구조변화에 의한 방향족 PBI/PI 블렌드의 상용성 및 상호작용의 세기(II) - DSDA로 합성한 PI들과의 블랜드들 -)

  • Ahn, Tae-Kwang
    • Applied Chemistry for Engineering
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    • v.9 no.2
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    • pp.207-213
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    • 1998
  • On the basis of the previous study[1], miscibility were investigated and intermolecular interaction strength for the miscibility were relatively compared for the blends poly{2,2-(m-phenylene)-5,5'-bibenzimidazole}(PBI) with two aromatic polyimides (PIs) synthesized by another dianhydride. Aromatic PAAs were prepared by the reaction of condensation of two diamines, 4,4'-methylene dianiline(4,4'-MDA) and 4,4'-oxydianiline(4,4'-ODA) with 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride(DSDA) using DMAc, and then converted into PIs after curing. PBI/PAA blends were prepared by solution blending. Cast films or precipitated powders of the PBI/PAA blends were cared at a high temperature to transform into PBI/PIs blends. Miscibility and specific intermolecular interaction for miscibility in the blends were investigated, and compared with previous polyimide structures of PBI/PIs blends [1]. Two blends, PBI/DSDA+4,4'-MDA(Blend-V) and PBI/DSDA+4,4'-ODA(Blend-VI), were found miscible : the evidences were optically clear films, synergistic single composition dependent $T_g{\prime}s$, and frequency shifts of N-H stretching band as much as $39{\sim}40cm^{-1}$, and of C=O stretching band near 1730 and $1780cm^{-1}$, 5~6 and $3{\sim}4cm^{-1}$, respectively. The specific intermolecular interactions existing between PBI and PIs were relatively analyzed with the area(A) formed between the $T_g{\prime}s$ of the measured and that of the calculated by the Fox equation at all compositions, the ${\kappa}$ values in Gordon-Taylor equation obtained from the measured $T_g{\prime}s$, and differences of the frequency shifts in the functional N-H and carbonyl stretching band. From the results, the area(A) and the ${\kappa}$ values for Blend-V and VI were smaller than those for Blend-III and IV used in previous study[1]. Differences of the frequency shifts in the functional groups(N-H and C=O) also showed similar tendency. Thus, specific intermolecular interaction strength in terms of hydrogen bonding of PBI/PI blends is dependent upon chemical structures of PIs, that is, PIs it seems that $SO_2$ group in dianhydride(DSDA) has weaker hydrogen bond strength than those of C=O in BTDA. In other words, it implies that the former occupied bulk space than the latter due to the sterric effect.

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A Study on Electronic Interaction in Dimetallic Complexes with Conjugated Chain (공액사슬로 연결된 이핵금속착체의 전자적 상호작용에 관한 연구)

  • Chung, Min-Chul;Munetaka Akita
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.17 no.6
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    • pp.652-660
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    • 2004
  • The cis-hex-3-ene-1,5-diynyl-bridged diiron compound 3, [(η$^{5}$ - $C_{5}$ M $e_{5}$ ) Fe(dppe)]$_2$($\mu$-C≡C-CH=CH-C≡C), have been prepared and characterized by cyclic voltammetry(CV), and electronic spectroscopy (UV-VIS and near-IR, NMR). From the results, compound 3 show two well resolved, single-electron, reversible oxidation waves by CV, and comproportionation constant(Kc) calculated from the CV data for compound 3. The Mixed-valence (MV) radical cation 3$^{+}$ show strong absorptions in the near IR, 1586 nm, and this band is more readily assigned as MV $\pi$-$\pi$ band of delocalized complex (Robin-Day Mixed-valence Class III), and the $H_{ab}$ , effective coupling parameter are most consistent with electronic delocalization.

A Real Time Low-Cost Hand Gesture Control System for Interaction with Mechanical Device (기계 장치와의 상호작용을 위한 실시간 저비용 손동작 제어 시스템)

  • Hwang, Tae-Hoon;Kim, Jin-Heon
    • Journal of IKEEE
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    • v.23 no.4
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    • pp.1423-1429
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    • 2019
  • Recently, a system that supports efficient interaction, a human machine interface (HMI), has become a hot topic. In this paper, we propose a new real time low-cost hand gesture control system as one of vehicle interaction methods. In order to reduce computation time, depth information was acquired using a time-of-flight (TOF) camera because it requires a large amount of computation when detecting hand regions using an RGB camera. In addition, fourier descriptor were used to reduce the learning model. Since the Fourier descriptor uses only a small number of points in the whole image, it is possible to miniaturize the learning model. In order to evaluate the performance of the proposed technique, we compared the speeds of desktop and raspberry pi2. Experimental results show that performance difference between small embedded and desktop is not significant. In the gesture recognition experiment, the recognition rate of 95.16% is confirmed.

A study of nonlinear interactions and optimum input parameters in all-optical phase-shift switches using ultrashort pulses with pulse-width less than 100fsec (100fsec이하의 극초단 광펄스를 사용하는 전광위상천이스위치에서 비선형상호작용 및 최적화 초기조건에 관한 연구)

  • Yoon, Ki-Hong;Song, Jae-Won
    • Journal of the Institute of Electronics Engineers of Korea SD
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    • v.39 no.6
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    • pp.8-18
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    • 2002
  • We study complicated nonlinear interactions of two orthogonally polarized pulses with pulse-width of less than 100fsec in the all-optical phase-shift switches, which use soliton pulse-train and fiber-splicing for control pulse to obtain multi-collisional $\pi$-phase-shift and consider Raman response function. We investigate switching performance in various input parameters such as input pulse-width and birefringence of fiber, and find optimum initial conditions for good switching performance in such all-optical switches.