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ESR 分光法에 의한 Anthraquinone 置換體의 음이온 라디칼에 대한 超微細 分離常數의 測定과 理論的 解釋
洪大一,金庚燦,金昌鎭,李甲龍 대구효성가톨릭대학교 자연과학연구소 1994 基礎科學硏究論集 Vol.1994 No.1
Anthraquinone 치환제인 1,4-DHAQ, 1,5-DHAQ, 1,8-DHAQ 및 1,8-DCAQ 등을 2-propanol(PoOH)과 triethylamine(TEA)의 혼합용매에 녹여 레이저 광환원 반응에 의하여 생성되는 세미퀴논의 음이온 라디칼을 ESR 분광기로 측정하였다. 또한 이들 치환체 라디칼의 초미세 구조선으로부터 초미세 분리상수를 얻어, 그 값을 이용한 컴퓨터 모의실험에 의하여 초미세분리상수(hfsc)를 결정하였다. 뿐만 아니라 측정된 ESR 스펙트럼의 초미세 분리상수를 지정하기 위하여 EHMO법으로 π스핀밀도를 계산하였다. Substituted anthrasemiquinone radical anions, which were formed by laser flash photo-reduction of the substituted anthraquinone(1,4-DHAQ, 1,5-DHAQ, 1,8-DHAQ, 1,8-DCAQ), were studied by the electron spin resonance spectroscopy in the mixed solvents of the 2-propanol and the triethylamine. Hyperfine splitting constants (hfsc) were determined by simulating the ESR spectra. Extended Hu¨ckel Molecular Orbital(EHMO) calculations were performed to obtain π spin densities for these quinones. The hyperfine splitting constants could be assigned to specific protons on the basis of π spin densities.
광화학 반응에서 생성된 Anthrasemiquinone Radical의 시간분해 ESR ; CIDEP에 관한 연구
홍대일,Hong Daeil,Kuwata Keiji 대한화학회 1990 대한화학회지 Vol.34 No.5
시간분해 ESR 분광법에서는 CIDEP법과 흡수 ESR 분광법을 사용하였다. 2-프로판올과 트리에틸아민 혼합용매에서 anthraquinone이 레이저 광선에 의해서 생성된 anthraquinone 라디칼 음이온을 시간분해 ESR 분광법으로 측정하였다. 이 semiquinone 라디칼은 대단히 안정하여 cw ESR을 측정할 수 있었다. 분극된 semiquinone 라디칼이 열적 평형상태로 소멸되는 속도상수는 스핀-격자 완화시간의 역수로서 2.6 ${\times}\;1-^5$ sec$^{-1}$이다. 그리고, 그 라디칼의 소멸속도상수는 300.0 sec$^{-1}$이다. CIDEP스펙트럼의 시간의존성에 대한 강도 변화는 마이크로파 출력이 강할수록 일반적으로 증가하였다. 그러나, 지나치게 출력을 높이면 감소 곡선상에 Torrey 진동이 뒷따라 일어났다. The time resolved electron spin resonance spectroscopy are used to two measurement methods of chemically induced dynamic electron polarization (CIDEP) and absorption ESR. The spectra of the semiquinone radical anion were successively detected in the laser flash photolysis of anthraquinone in the mixtures of 2-propanol and triethylamine. The semiquinone radical anion was fairly stable and its cw ESR could be observed. The rate constant (T1$^{-1}$) of the spin-depolarization of polarized semiquinone radical anion was 2.6 ${\times}\;1-^5$ sec$^{-1}$ and the decay of the radical anion was the first order with the rate constant (K$_1}$) of 300.0 sec$^{-1}$. The intensity of CIDEP spectra increased with the increasing the microwave power, but the Torrey wiggles appeared following with decay curves.
열처리공학회지,제27권 제1호(2014) : GZO/ZnO 적층박막의 두께변화에 따른 구조적, 전기적, 광학적 물성 변화
김승홍 ( Seung Hong Gong ),김선경 ( Dong Kyung Kim ),김소영 ( So Young Kim ),전재현 ( Jae Hyun Jeon ),공태경 ( Tae Kyung Gong ),최동혁 ( Dong Hyuk Choi ),손동일 ( Dong Ll Son ),김대일 ( Daeil Kim ) 한국열처리공학회 2014 熱處理工學會誌 Vol.27 No.1
Ga doped ZnO (GZO) single layer and GZO/ZnO bi-Iayered films were deposited on glass substrates by radio frequency magnetron sputtering and then the influence of film thickness on the structural, electrical. and optical properties of the films was considered, Thicknesses of the GZO/ZnO films was varied as GZO 100 nm, GZO 85 nm/ZnO 15 nm and GZO 70 nm/ZnO 30 nm, respectively The observed result means that optical transmittance and electrical resistivity of the films were influenced with film thickness and GZO 85 nm/ZnO 15 nm bilayered films show the higher figure of merit than that of the films prepared other films in this study,
Effects of Electron Irradiation on the Properties of ZnO Thin Films
Kim, Seung-Hong,Kim, Sun-Kyung,Kim, So-Young,Kim, Daeil,Choi, Dae-Han,Lee, Byung-Hoon,Kim, Min-Gyu The Korean Institute of Electrical and Electronic 2013 Transactions on Electrical and Electronic Material Vol.14 No.4
ZnO films were deposited on glass substrates by radio frequency (RF) magnetron sputtering and exposed to intense electron beam irradiation to investigate the effects of electron irradiation on the properties of the films. Although all of the films had ZnO (002) textured structure regardless of electron irradiation, the grain sizes of the films decreased with electron irradiation. Surface roughness also depended on electron irradiation. The surface roughness varied between 2.3 and 1.6 nm, depending on the irradiation energy. Based on photoluminescence (PL) characterization, the most intense UV emission was observed from ZnO films irradiated at 900 eV. Since the intensity of UV emission is dependent upon the stoichiometric of ZnO films, we conclude that 900 eV was the optimum electron irradiation energy to achieve the best stoichiometric of ZnO films in this study.
ESR 및 TRESR 分光法에 의한 Phenanthrenequinone의 光環元反應(I). Radical의 超微細分離常數에 미치는 溶媒效果
홍대일,김창진,Daeil Hong,Chang Jin Kim 대한화학회 1993 대한화학회지 Vol.37 No.3
유기용매인 2-propanol, 2-pentanol 또는 benzene에 triethylamine을 혼합시켜 phenanthrenequinone을 포화시킨 용액에 Excimer laser(XeCl)를 쪼인 광환원반응에서 생성된 음이온 라디칼의 초미세 분리상수 전자스핀 공명분광법과 시간분애 전자스핀 공명분광법을 이용하여 얻었다. 그 결과 초미세분리상수 A$_{H1}$과 A$_{H2}$는 2-propanol에서 1.662, 0.378, 2-pentanol에서 1.602, 0.361 G이었고, benzene에서는 A$_{H1}$은 1.518이었다. 이와같이 혼합용매의 극성이 감소함에 따라 초미세 분리상수는 감소하였고, 비극성인 벤젠 혼합용매하에서는 자기적 등가양성자에 의한 작은 초미세분리(A$_{H2}$)는 측정할 수 없었다. 특히 2-pentanol과 triethylamine과의 3:1 혼합용매하에서 trietylamine radical(TEA${\cdot}$)이 0.15~0.30${\mu}s$ 시간범위의 시간분해 전자스핀공명 스펙트럼에서 phenanthrenequinone 음이온 라디칼과 함께 측정되었다. 이와같은 용매효과의 시간분해 전자스핀공명 스펙트럼의 측정 결과로부터 불안정한 짧은 수명의 반응중간체인 스핀편극된 phenanthrenequinone 음이온 라디칼(*PQ${\cdot}^-$)의 존재를 알 수 있었고, 각 혼합용매에서 초미세분리상수를 얻었다 The hyperfine splitting constants of phenanthrenequinone anion radical have been determined for the solution of triethylamine with 2-propanol, 2-pentanol or benzene by cwESR and time-resolved ESR methods. The radical anion was produced by photolysis using a pulsed excimer laser. The resulting hyperfine splitting constant A$_{H1}$ and A$_{H2}$ are 1.662, 0.378 in 2-propanol, 1.602, 0.361 in 2-pentanol and 1.518 in benzene respectively. The hyperfine coupling constants decrease with the decreasing of polarity of the mixed solvent. The tendency of the variation depends on the polarity of the solvents, thus, making it in impossible to observe the magnetic equivalent proton in a mixed solvent of nonpolar benzene. Particularly, time-resolved ESR spectrum of triethylamine radical (TEA${\cdot}$) has been observed in 0.15∼0.30 ${\mu}s$ from the solvent of 3 : 1 with 2-pentanol and triethylamine. Thus from the results of solvent effect, we can suggest that the identification of the unstable short-lived spin polarized phenanthrenequinone anion radical(*PQ${\cdot}^-$) proceed through photochemistry.
Moon, Youngtaek,Kwon, Daeil,Hong, Sungwoo WILEY‐VCH Verlag 2012 Angewandte Chemie Vol.124 No.45
<P><B>Mit einer Tandemsequenz</B> (siehe Schema) gelingt in einem einzigen Synthesegang die Einführung einer Enon‐Funktionalität durch Dehydrierung und die anschließende Kreuzkupplung der Zwischenstufe. Der Prozess erzeugt hoch funktionalisierte cyclische Enolone und Enaminone aus einfach zugänglichen heterocyclischen Ketonen.</P>
TRESR 분광법에 의한 Phenanthrenequinone의 광환원반응(Ⅱ) -Radial의 스핀-격자 완화시간에 미치는 점성도효과
金昌鎭,洪大一 大邱大學校附設 基礎科學硏究所 1998 基礎科學硏究 Vol.15 No.2
The Phenanthrenequinone anion radical(PQ·-) was produced by photolysis using a pulsed N₂ laser in the mixed solvent of 2-propanol,2-pentanol or benzene and triethylamine(TEA). Particularly,time-resolved ESR spectrum of PQ·- and TEA radical( CH₃CHN(C₂H_(5))₂) has been obsered at 0.13-0.30 μs in the 3:1 mixed solvent of 2-pentanol and TEA. The spin-lattice relaxation time(T₁) has increased exponentially with the increasing of mixed solvents viscosity , it was affected by the spin rotational and diffusion rate of radicals due to the viscosity and solvation of solvent. The log plot of the relaxation time versus the viscosity gave the straight lines with different slope. This fact may be supposed that both PQ·- and TEA radical have contributed to spin-lattice relaxation time in the 3:1 mixed solvent of 2-pentanol and triethylamine.
Moon, Young Sun,Kim, Daeil,Lee, Geumbee,Hong, Soo Yeong,Kim, Kuk Ki,Park, Seung Min,Ha, Jeong Sook Elsevier 2015 Carbon Vol.81 No.-
<P><B>Abstract</B></P> <P>We report on the facile fabrication of an all-solid-state flexible planar-type micro-supercapacitor (MSC) array with micropatterned hybrid electrodes of graphene foam (GF)/COOH-functionalized multi-walled nanotubes (MWNT-COOH)/MnO<I> <SUB>x</SUB> </I> and its application as a power source to operate various micro-light emitting diodes ( μ -LEDs) and a SnO<SUB>2</SUB> nanowire (NW) UV sensor. Composite electrodes of GF/MWNT-COOH/MnO<I> <SUB>x</SUB> </I> were simply micropatterned via reactive ion etching (RIE) with a metal mask, and used as current collectors as well as active materials. Polyvinyl alcohol-H<SUB>3</SUB>PO<SUB>4</SUB> was used as the solid-state electrolyte. The use of the composite film electrodes increased the area specific capacitance ∼11 times compared to the MSC with just patterned GF electrodes. After 10<SUP>4</SUP> charge/discharge cycles, 89.5% of the initial capacitance was maintained. Furthermore, very stable performance was observed over 10<SUP>3</SUP> bending of the whole MSC on a polyethersulfone substrate with capacitance retention of 95.5%. For the first time, we could directly measure the UV-induced photocurrent through a SnO<SUB>2</SUB> NW sensor powered by 4 MSCs connected in parallel. Fast response to UV pulses was detected for a time of more than 10min. This work demonstrates the high application potential of our MSCs using patterned electrodes of GF/MWNT-COOH/MnO<I> <SUB>x</SUB> </I> to self-powered flexible electronic devices including NW-based sensors.</P>