• Title/Summary/Keyword: $NdCl_3$

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Kinetics and Mechanism of the Anilinolysis of Dicyclohexyl Phosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1997-2002
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    • 2011
  • The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; $cHex_2$P(=O)Cl] with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 60.0 $^{\circ}C$. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal ($k_H/k_D$ > 1; max $k_H/k_D$ = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse ($k_H/k_D$ < 1; min $k_H/k_D$ = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted $S_N2$ mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.

Synthesis and Characterization of Tetrathiafulvalene (TTF) and 7,7,8,8-Tetracyanoquinodimethane (TCNQ) Compounds with PdX2(X=CI, NO3and Hexafluoroacetylacetonate)

  • Kim, Young-Inn;Jeong, Chan-Kyou;Lee, Yong-Min;Choi, Sung-Nak
    • Bulletin of the Korean Chemical Society
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    • v.23 no.12
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    • pp.1754-1758
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    • 2002
  • Tetrathiafulvalene(TTF) reacts with $PdCl_2,Pd(NO_3)_2$ and $Pd(hfacac)_2$(hexafluoroacetylacetonate) in ethanol to give $(TTF)_{1.5}PdCl_2$ (1a), $(TTF)_3Pd(NO_3)_2$ (1b) and $(TTF)_4Pd(hfacas)_2$ nd (1c), respectively. $PdCl(TCNQ)_{2.5}{\cdot}CH_3OH(2a)$was obtained from the reaction of $PdCl_2$ with LiTCNQ in methanol via the partial replacement of $Cl^-$ in $PdCl_2$ by $TCNQ^-$anion, whereas the total substitution of the labile $NO_3^-$ in $Pd(NO_3)_2$ yielded pd(TCNQ)·$CH_3OH$ (2b). $Pd(hfacac)_2(TCNQ)_2\cdot3CH_3OH$ (2c) was obtained from $Pd(hfacac)_2$ and LiTCNQ in methanol. The prepared compounds were characterized by spectroscopic (IR, UV, XPS) methods and magnetic (EPR, magnetic susceptibility) studies. The powdered electrical conductivities (${\sigma}_{rt}$) of the prepared compounds at room temperature were about~$10^{-7}S{\cdot}cm^{-1}$. The effective magnetic moments were lass than the spin-only value of one unpaired electron and no EPR signals from Pd metal ions were observed in any of the compounds, indicating that the Pd ions were diamagnetic and the magnetic moments arose from$(TTF)_n$ or $(TCNQ)_n$ moieties. The experimental evidences revealed that the charge transfer had occurred form $(TTF)_n$ moiety to the central Pd metal ion in 1a, 1b and 1c. Thus the TTF donors were ions in 2a and 2b were diamagnetic Pd(II) oxidation state. In contrast, the Pd metal ion was oxidized to Pd(IV) state in 2c as a result of an addition of $TCNQ^-$anion to $Pd(hfacac)_2$ in methanol. The oxidation states of the Pd metal ions were confirmed using the x-ray photoelectron spectroscopy.

Synthesis and Photo Luminescent Characteristics of SrAl2O4:Eu2+,Dy3+ Phosphor using Polymer Matrix (폴리머 매트릭스를 전구체로 사용한 SrAl2O4:Eu2+,Dy3+ 축광성 형광체의 합성 및 형광 특성)

  • Kim, Soo-Jong;Kwon, Hyuk-Sil
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.20 no.8
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    • pp.671-679
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    • 2007
  • [ $SrAl_2O_4:Eu^{2+},\;Dy^{3+}$ ] phosphor was synthesized using the impregnation method, and its photoluminescence and long-afterglow properties were investigated, A mixture of $Sr(NO_3)_2,\;Al(NO_3)_2\;9H_2O,\;EuCl_3\;6H_2O,\;DyCl_3\;6H_2O,\;NdCl_3\;6H_2O$ salts were dissolved in distilled water and impregnating into the polymer precursor. After drying, the impregnated mixture was heat treated at $900-1400^{\circ}C$ for 2h in a $N_2-H_2$ reduction atmosphere. The microstructure and crystal structure of the $SrAl_2O_4:Eu^{2+},\;Dy^{3+}$ powders were examined by scanning electron microscopy and X-ray diffraction, respectively. The photoluminescence spectra showed an excitation band along over wide wavelength of 250-450nm, and a broaden emission with a maxima peak at 360nm. In addition, the spectra also showed a good long after glow that decayed over a 1000sec period after 10 min excitation illumination.

Wavelength tunability of XeCl laser pumped double-resonator dye laser for DIAL (DIAL용 XeCl 레이저펌핑 쌍공진기색소레이저의 파장가변특성)

  • 이용우;이주희
    • Korean Journal of Optics and Photonics
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    • v.7 no.3
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    • pp.238-243
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    • 1996
  • We have developed XeCl laser pumped double-resonator Dye laser and two-stage amplifier system, and generated simultaneously of alternatively two wavelengths suitable in DIAL system. The developed double-resonator is composed of 1st and 2nd diffraction orders on light incidence angle in grazing-incidence grating method with 1200 g/mm. We have obtained spectral linewidth below 10 pm and the total efficiency dependent on pump energy over 6%. The tuning ranges dependent on 1st and 2nd diffraction orders are 434~470 nm and 436~468 nm, respectively. The amplification gain and rine-450 dye laser by using the double-resonator laser system and measured the distribution of $NO_2$ concentration over Suwon as the result of transmission of laser output of 6 mJ in this DIAL system. Consequently, we have confirmed that the developed dye laser system is very useful as the tunable source for DIAL.

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Effects of stress induced by changes of water temperature on the non-specific defense mechanism in cultured olive flounder, Paralichthys olivaceus (수온 변동 자극이 양식 넙치, Paralichthys olivaceus의 비특이적 생체 방어에 미치는 영향)

  • Lee, Deok-Chan;Kim, Do-Hyung;Kim, Su-Mi;Kang, Myong-Seok;Hong, Mi-Ju;Kim, Hyun-Jeong;Park, Soo-Il
    • Journal of fish pathology
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    • v.15 no.2
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    • pp.65-75
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    • 2002
  • This study was performed to know the effects of stress induced by the daily fluctuation of water temperture from 18$^{\circ}C$ to 25$^{\circ}C$ up and down for 30 days on the defence mechanism of olive flounder. Puralichthys olivaceus. To make clear the temperature stress on the defense mechanism of the tested fish. several factors of immune response such as counting of leucocyte appearance in peripheral blood, phagocytic activity in whole blood cells, nitroblue tetrazolium(NBT) reduction, chemiluminescence(CL) response, and lysozyme activity were investigated at 28 days after giving the change of water temperature. The fish was controlled under the none feeding condition during experimental period. Mortality of the tested fish was rapidly increased up to 22% within the first one week of the experimental period without any additional stress factors. The number of neutrophil of peripheral blood in the tested group was significantly higher than the control group at the 2nd week. but the number of lymphocyte was significantly lower than the control group at the 1st and 3rd day of the experimental period. respectively. In the NBT reduction test, the activity of macrophage in the control group fish was the highest on the 7th day while that in the tested group was on the 3rd day. Also. the phagocytosis of tested group against formalin killed cells was retarded compared with the control. CL response of the tested group was significantly lower from 2nd to 5lh day of the experimental period than the control. 'The lysozyme activity of tested group was remained higher during the experimental period than the control. Even though the tested fish showed different results in some non-specific factors of immune respceses between tested and control group fish, olive flounder seems highly adaptable in repealed water temperature change in condition after one week under the given temperature fluctuation range.

Evaluation of Groundwater Quality Using Factor Aanlyses and Agrochemicals in an Agricultural Area (요인분석과 농약성분 특성에 의한 농업지역의 지하수 수질 평가)

  • Lee, Jeong-Hwan;Hamm, Se-Yeong;Kim, Kwang-Sung;Cheong, Jae-Yeol;Ryu, Sang-Min;Kim, Deuk-Ho;Kim, Hyun-Ji
    • Economic and Environmental Geology
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    • v.42 no.3
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    • pp.217-234
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    • 2009
  • This study characterized groundwater quality and the influence of agrochemicals in a part of Ilgwang-Myeon agricultural area in Gijang-Gun, Busan Metropolitan City, using factor analyses. From the 1st, 2nd, and 3rd analyses of groundwater samples, the mean concentrations of $Ca^{2+}$, $Na^+$, $Mg^{2+}$, $K^+$, $Zn^{2+}$, $Cu^{2+}$, $Fe^{2+}$, $Al^{3+}$, $NO_3\;^-$, $Cl^-$, $SO_4\;^{2-}$, $F^-$, and $SiO_2$ were higher in the 2nd analysis than the other analyses. Pesticide carbofuran and herbicide alachlor were detected at the wells more than a half of all the wells in the 2nd analysis but not in the 4th analysis. This fact may be explained by that a higher precipitation induced higher infiltration rate of contaminants into groundwater during the 2nd survey. According to R- and Q-mode factor analyses, and chemical composition, inorganic constituents excepting $SiO_2$, $HC0_3\;^-$-, and $F^-$ may be influenced by anthropogenic sources (manures, synthetic fertilizers, and domestic wastes), seawater as well as water-mineral interaction. A typical indicator of groundwater contamination, nitrate, exceeds around 4-5 times over the Korean standard for drinking water. Additionally, the influence of seawater diminishes from the seaside to inland.

The Influence of the Changing of Cyclic Frequency on the Corrosion Fatigue Fracture Behavior of the Dual Phase Steel in 3% NaCl Solution (3% NaCl 수용액중에서 복합조직강의 부식피로 파괴거동에 미치는 주파수변화의 영향)

  • O, Se-Uk;Sin, Gyu-Dong;Kim, Ung-Jip
    • Journal of Ocean Engineering and Technology
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    • v.9 no.2
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    • pp.141-148
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    • 1995
  • Fatigue tests were carried out by a rotary bending testing machine of cantilever type. M.E.F.(ferrite encapsulated islands of martensite) materials were made by a series of heat treatment from a low carbon steel(SM 20 C). The fatigue tests were conducted at stress levels of 302 MPa and with frequencies of 25Hz, 2.5 Hz and 0.5 Hz in 3% NaCl solution. The fatigue strength increased with frequency got higher. The microcracks and corrosion pits were generated at the boundary between the matrix and the 2nd phase. The cracks generated by the corrosion pits were coalesced with the pits around the notch and became the initial crack. The $N_i/N_f$ ratio increased as the frequency and stress level decreased. The interference phenomenon increased with stress level and frequency gots higher. The crack propagation rate was delayed as the stress level lowers and the frequency gets higher, however, the range of the stress intensity factor depended only on a stress level.

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Electrochemical polishing method using the point electrode tools(2nd) (점 전극을 이용한 전해연마 가공특성)

  • 이승훈;박규열;양순용
    • Proceedings of the Korean Society of Machine Tool Engineers Conference
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    • 1999.05a
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    • pp.251-255
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    • 1999
  • In last paper, it was suggested electrochemical polishing method using the point electrode tools. It was aimed that Machining rate in ECM using the point electrode method should be ultimately small and also high dimension accuracy and surface integrity should be fine. In this paper, the machining characteristics were investigated by using the several types of electrolyte.

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The Effects of Ambient Ions on the Growth of Gold Nanoparticles by Laser Ablation in Liquid

  • Kwon, Hyejin;Kim, Kuk Ki;Song, Jae Kyu;Park, Seung Min
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.865-870
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    • 2014
  • Gold nanoparticles (AuNPs) were synthesized by laser (Nd:YAG, ${\lambda}$ = 1064 nm) ablation of a gold target immersed in various aqueous electrolyte solutions (7 mM of LiCl, NaCl, KCl, NaBr, and NaI) as well as in deionized water. The surface plasmon absorption and EDX of AuNPs so produced as well as their TEM images were analyzed to investigate the effects of ambient ions on the growth and aggregation of NPs. The size of AuNPs was reduced by laser ablation in the presence of chloride and bromide ions while it increased drastically when AuNPs were formed in iodide solution. Interestingly, triangular nanoplates were synthesized only in iodide solution. Surface chemistry on AuNPs in various electrolyte solutions was explored to elucidate the role of ions on the size and stability of AuNPs.

The Effect of Rapidly Rotating Shift work on the Fatigue Level, Urinary 17-KS, $Na^+$ and $Cl^-$ Excretion (빠른 교대근무가 피로도, 요중 17-KS, $Na^+,\;Cl^-$ 배설에 미치는 영향)

  • Jung, Young-Ju
    • Journal of Korean Biological Nursing Science
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    • v.1 no.1
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    • pp.100-114
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    • 1999
  • This study was done to investigate the effects of rapidly-rotating shift work of two-day interval on fatigue level and the concentration of urinary 17-KS, $Na^+,\;Cl^-$. The subjects were 20 nursing college students(control group) and 15 nurses in a university hospital and the study was done from Apr. 21 to May 4th, 1999. In the test group, each 5 nurses were allocated to day shift(8 AM-4 PM), evening shift(4 PM-12 MN) and night shift(12 MN-8 AM) respectively. The fatigue level were measured 30 minutes after work start on the 2nd day of work shift. Urine specimens were collected at 8 AM, 4 PM and 12 MN on the 2nd day of work shift in the control group and 30 minutes before and after work on the 2nd day of work shift in the test group. The data were analyzed with SPSS(for Window, ver 7.5). Statistical analysis was performed by using t-test, paired t-test and ANOVA. The results were as follows. 1. The perceived fatigue level in shift work 1) The physical and mental fatigue level were significantly higher in night shift than that in day or evening shift(p<0.05). In the neuro-sensory fatigue level, night shift showed higher tendency than that in day or evening shift, but there were no significant differences between each shifts. 2) Comparison between the control group and the test group: Physical fatigue level was significantly higher in night shift than that in day or evening shift of the control group(P<.001). Mental fatigue level was significantly higher in day or night shift than that in evening shift of the control group(P<.05). In the neuro-sensory fatigue level, test group showed higher tendency than that in the control group, but there were no significant differences between two groups. 3) The total fatigue level was higher in night shift than that in day shift or evening shift(P<.05). In comparing with the control group, night shift and day shift showed higher total fatigue level than that in the control group(p<0.05). 2. The concentration of urinary 17-KS, $Na^+$ and $Cl^-$ In the control group, urinary 17-KS, $Na^+$ and $Cl^-$ showed higher level in afternoon that in morning and night. In the test group, cr in day and evening shift and $Na^+$ in evening shift showed higher level at the end of work. The 17-KS concentration at the begining and the end of work in three shift groups were lower than those in control group(p<0.05), however, $Cl^-$ concentration at the begining of work in day shift, and the end of work in day and evening shift were higher than those in control group(p<0.05). $Cl^-$ concentration at the begining and end of work in night shift were considerably higher than those in control group repectively(p<0.1, p<001). $Na^+$ concentration showed a higher tendency in three shift groups except at the begining of work in night shift, but there were no statistical difference. In comparing concentration of the 17-KS, $Na^+$ and $Cl^-$ among the shift groups, 17-KS concentration showed a lower tendency and $Na^+,\;Cl^-$ showed a higher tendency in night shift: The result of this study showes that biorhythm of shift work nurse was irregular. Fatigue level as the subjective index for evaluating the health problem concerning shift work was higher in night shift and proved to be in accordance with the concentration of urinary 17-KS, $Na^+$ and $Cl^-$ used as objective indices. Disturbation of biorhythm and work stress due to night shift seems to cause the health problem of nurses and decrease of work efficiency. It is considered that work regualtion is necessary for the rational management of the nursing administration.

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