• Title/Summary/Keyword: p.f. ring

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$^{13}C-^{1}H$ Coupling Constant as a Criterion for the Presence of $\pi$ Bridging in Substituted 9-Benzonorbornenyl Cation

  • Gweon-Young Ryu;Jung-Hyu Shin
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.546-548
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    • 1993
  • The discrete structure of substituted 9-benzonorbornenyl cation 3a and 3c was studied using the empirical ${\Delta}$J equation which was developed by Kelly and coworker$^5$. The ${\Delta}$J values of substituted 9-benzonorbornenyl cations were obtained from p-methyl-6,7-dimethyl benzonorbornen-9-yl (3a) and 9-methyl-6,7-dimethyl benzonorbonen-9-yl (3c) cations under stable ion conditions, and were compared with those of the corresponding ketone analog; these cations were generated by dissolving the corresponding carbinols in superacid at -120$^{\circ}$C and the nmr spectra taken at -60$^{\circ}$C~-90$^{\circ}$C. The ${\Delta}$J values are 8.7 Hz for the bridgehead carbons in cation 3c and 3.1 Hz for cation 3b. The ${\Delta}$J values at C5,8 in fused benzene ring are 14.3 Hz for cation 3c and 8.7 Hz for cation 3a. The excellent correlation of the ${\Delta}$J values with 1$^9F$ chemical shifts of p-fluorophenyl-6,7-dimethylbenzonorbornenyl cation (3d) indicate that ${\Delta}$J value is a reliable probe to charge density at adjacent cationic carbon. These NMR parameters strongly support that the symmetrically ${\pi}$-bridged nonclassical structure (type 2) of substituted 9-benzonorbornenyl cations in stable ion conditions.

A Study on Optimization of Spray Type Flue Gas Desulfurization (FGD) System (모사 탈황흡수탑을 이용한 Spray Type 탈황설비 최적운전 방안에 관한 연구)

  • An, Hi-Soo;Park, Seung-Soo;Kim, Ki-Hyoung;Kim, Young-Ho
    • Applied Chemistry for Engineering
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    • v.18 no.1
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    • pp.29-35
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    • 2007
  • Recently, due to narrow margin on design factor of flue gas desulfurization (FGD) systems or aging of systems, some problems such as decrease of $SO_2$ removal efficiency and difficulty on coping with unstable state are arising on FGD systems. On this study, to cope with these problems several methods such as adjustment of reagent pH, inlet $SO_2$ concentration, variation of units of operation pump, installation of liquid distribution ring (LDR) were attempted to increase the $SO_2$ removal using spray type simulated FGD system. Also, sulfite and Al/Fx ion effects on limestone blinding were experimented. When three absorber recirculation pumps were operated, $SO_2$ removal was increased by 12% in comparison with that of two pumps operation. $SO_2$ removal was increased by 2~7% after installation of LDR. Dissolved oxygen increased up to 0.5 ppm and limestone binding effect was alleviated after injection of dibasic acid (DBA) with the concentration of 500 and 1,000 ppm. When $Al^{3+}$ and $F^-$ ions were coexisting, the dissolution rate of limestone was decreased by 20%.

A Study on the Toothbrush-Dentifrice Abrasion of Class V Restroations (치경부 5급 와동 수복의 잇솔질 마모에 관한 연구)

  • Hwang, Su-Jin;Yu, Mi-Kyung;Lee, Kwang-Won
    • Journal of Dental Rehabilitation and Applied Science
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    • v.21 no.1
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    • pp.69-81
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    • 2005
  • The objective of this study was to evaluate the toothbrush abrasion characteristics of class V restorations. Thirty extracted human premolars, which were collected from oral surgery clinics were used. We mounted five teeth in a metal ring mold of 50 mm in diameter and 15 mm in height using chemically cured acrylic resin. Class V cavities were prepared in lingual cervical root surfaces and restored using one of following restorative materials : Dentin Conditioner/Fuji II LC (Group FL), All Bond II/Z-250 (Group ZT), One-up Bond F/Palfigue Estelite (Group PE), F2000 Primer/Adhesive (Group FT), and Prime & Bond 2.1/Dyract AP (Group DR). They were stored under distilled water at $37^{\circ}C$ for seven days. The toothbrush abrasion test was conducted using a wear testing machine of pin-on disk type under a load of 1.5 N for 100,000 cycles. We have examined the bonded interfaces, the changes of surface roughness and color of abraded surfaces. From this experiment, the following results were obtained. 1. The change of surface roughness showed high degree: RMGIC>compomer>composite resin (p<0.05). 2. Because of the protrusion and missing of filler particles, SEM observation of abraded surfaces of RMGIC and compomers revealed the increase of surface roughness due to the selective removal of matrix resin. 3. The color change by toothbrush abrasion was affected in large part by the change of $L^*$ and $b^*$ of resin composites (p<0.05). 4. The color change by toothbrush abrasion was so small to detect by human eyes. 5. SEM observation of abraded surfaces revealed the interface bonding was the best in the FT group.

Preparation and Structure of $[Cu(L)]I_2\cdot2H_2O(L: 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,$0^{1.18},0^{7.12}$]docosane) ($[Cu(L)]I_2\cdot2H_2O(L: 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,$0^{1.18},0^{7.12}$docosane) 착물의 합성 및 구조)

  • Choe, Gi-Yeong;Kim, Dong-Un;Seo, Il-Hwan
    • Korean Journal of Crystallography
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    • v.9 no.1
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    • pp.1-5
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    • 1998
  • The complex[Cu(L)I2, 2H2O(1) (L:3,14-Dimethyl-2,6,13,17-tetraazatricyclo [14,4,01.18, 07.12]docosane) has been prepared and structurally characterized. The complex (1) crystallizes in the triclinic system, space group P1, a=8.400(1)Å, b=8.986(3) Å, c=9.156(1) Å, α=82.42(1)˚, β=73.61(1)˚ λ=81.04(2)˚, Z=1, R for 1926 observed reflections of [F0>40(F0)], measured at 288K, was 0.042. The tetracoordination around Cu atom of complex(1) is square plane and the average bond distance of Cu-N is 2.029 (11) Å. Both six-membered chelate rings adopts a chair conformation and the five-membered ring are gauche with the sec-NH centers having the RRSS configuration.

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Fingerprint of Carcinogenic Semi-Volatile Organic Compounds (SVOCs) during Bonfire Night

  • Pongpiachan, Siwatt
    • Asian Pacific Journal of Cancer Prevention
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    • v.14 no.5
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    • pp.3243-3254
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    • 2013
  • It is well known that increased incidences of lung, skin, and bladder cancers are associated with occupational exposure to PAHs. Animal studies show that certain PAHs also can affect the hematopoietic and immune systems and can produce reproductive, neurologic, and developmental effects. As a consequence, several studies have been attempted to investigate the fate of PAHs in atmospheric environment during the past decades. However, there is still a lack of information in regard to the atmospheric concentration of PAHs during the "Bon Fire Night". In this study, twenty-three polycyclic aromatic hydrocarbons and twenty-eight aliphatics were identified and quantified in the $PM_{10}$ and vapour range in Birmingham ($27^{th}$ November 2001-$19^{th}$ January 2004). The measured concentrations of total particulate and vapour (P+V) PAHs were consistently higher at the BROS in both winter and summer. Arithmetic mean total (P+V) PAH concentrations were $51.04{\pm}47.62$ ng $m^{-3}$ and $22.30{\pm}19.18$ ng $m^{-3}$ at the Bristol Road Observatory Site (BROS) and Elms Road Observatory Site (EROS) respectively. In addition arithmetic mean total (P+V) B[a]P concentrations at the BROS were $0.47{\pm}0.39$ ng $m^{-3}$ which exceeded the EPAQS air quality standard of 0.25 ng $m^{-3}$. On the other hand, the arithmetic mean total (P+V) aliphatics were $81.80{\pm}69.58$ ng $m^{-3}$ and $48.00{\pm}35.38$ ng $m^{-3}$ at the BROS and EROS in that order. The lowest average of CPI and $C_{max}$ measured at the BROS supports the idea of traffic emissions being a principle source of SVOCs in an urban atmosphere. The annual trend of PAHs was investigated by using an independent t-test and oneway independent ANOVA analysis. Generally, there is no evidence of a significant decline of heavier MW PAHs from the two data sets, with only Ac, Fl, Ph, An, 2-MePh, 1+9-MePh, Fluo and B[b+j+k]F showing a statistically significant decline (p<0.05). A further attempt for statistical analysis had been conducted by dividing the data set into three groups (i.e. 2000, 2001-2002 and 2003-2004). For lighter MW compounds a significant level of decline was observed by using one-way independent ANOVA analysis. Since the annual mean of $O_3$ measured in Birmingham City Centre from 2001 to 2004 increased significantly (p<0.05), it may be possible to attribute the annul reduction of more volatile PAHs to the enhanced level of annual average $O_3$. By contrast, the heavier MW PAHs measured at the BROS did not show any significant annual reduction, implying the difficulties of 5- and 6-ring PAHs to be subject to photochemical decomposition. The deviation of SVOCs profile measured at the EROS was visually confirmed during the "Bonfire Night" festival closest to the $6^{th}$ November 2003. In this study, the atmospheric PAH concentrations were generally elevated on this day with concentrations of Fl, Ac, B[a]A, B[b+j+k]F, Ind and B[g,h,i]P being particularly high.

The Solvent-Independent Structure of 6-(2-pyridyl)-3, 5-hexadiyn-1-ol (6-(2-pyridyl)-3, 5-hexadiyn-1-ol의 용매 비의존 분자구조)

  • 서일환;이진호
    • Korean Journal of Crystallography
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    • v.6 no.1
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    • pp.36-42
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    • 1995
  • Two types of single crystals of the title compound [6-(2-pyridyl)-3, 5-hexadiyn-ol, PyHxD] were obtained by solution of n-hexane/CH2C12 and n-hexane/Et2O, and their molecular conformations are proved identical in spite of different of space groups; C22H18N2O2 (I), Mr=343.70, Monoclinic, Pa, a=14.595(2), b=5.413(2), c=12.218(2)Å, β=96.86(1)°, V=958.3Å3, Z=2, Dx=1.19 Mgm-3, λ(MoKα)=0.71069Å, μ=0.072mm-1, F(000)=360.0, T=292K, R=0.104 for 756 unique observed reflections. An asymmetric unit contains a dimer connected by two N-H…O intermolecular hydrogen bonds. C11H9NO (II), Mr=171.85, Monoclinic, P21/a, a=14.611(2), b=5.423(6), c=12.191(2)Å, β=96.89(1)°, V=959.0Å3, Z=4, Dx=1.19 Mgm-3, λ(MoKα)=0.71069Å, μ=0.072mm-1, F(000)=360.0, T=293K, R=0.066 for 824 unique observed reflection. The structural asymmetric unit contains a molecule, but two N-H…O hydrogen bonds related by controsymmetry make the molecules form a dimer. In both structure, the dihedral angle between the planar pyridyl ring and the plane defined by C(10)-C(11)-O connected by linear diyne chain is approximately normal, and the molecules are stacked along b-axis with the unit repeat of b-axis.

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Studies on the Dissociation Constant of Benzoic Acid and Substituted Benzoic Acids in Methanol-Water Mixtures by Conductometric Method (메탄올-물 혼합용매에서 전도도법에 의한 벤조산 및 치환된 벤조산의 해리에 관한 연구)

  • Min Soo Cho;Hyoung Ryun Park;Soon Ki Rhee;Kye Soo Lee;Bon Su Lee
    • Journal of the Korean Chemical Society
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    • v.35 no.3
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    • pp.196-203
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    • 1991
  • The $pK_a$ values of benzoic acid and meta, para-halogen substituted benzoic acids in MeOH-$H_2O$ mixtures (0∼80% of MeOH) have been determined at 25$^{\circ}$C using a conductometric method on the basis of the Fuoss-Kraus equation, and further verified using modified conductometric method of Gelb. The dependence of $pK_a$ on halogen substituents has been discussed in terms of substituent-constant (${\sigma}$), which is devided into electron-withdrawing inductive contribution (${\sigma}_1$) and electron-donating ${\pi}$-resonance one (${\sigma}_R$). The linear-dependence of ${\sigma}_1$'s on $D^{-1}$ with positive slope and that of ${\sigma}_R$'s on $D^{-1}$ with negative slope have been interpreted on the basis of field effect and through-space interaction of ${\pi}$-lone pair of halogen substituent and ionization center via ${\pi}$-system of benzene ring.

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Long Term Average Spectrum Characteristics of Head and Chest Register Sounds of Western Operatic Singers : Extended Study (성악다들의 목소리에 대한 Long Term Average Spectrum 분석 -$2^{nd}$ Singer's Formant의 존재 가능성에 대하여-)

  • Ban, Jae-Ho;Kwon, Young-Kyung;Jin, Sung-Min
    • Journal of the Korean Society of Laryngology, Phoniatrics and Logopedics
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    • v.15 no.1
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    • pp.31-36
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    • 2004
  • Background and Objectives : It has been shown that the epilaryngeal tube in the human airway is responsible for vocal ring, or the singer's formant. In previous study, authors showed that in trained tenors, besides the conventional singer's formant in the region of ,5500Hz, another energy peak was observed in the region of 8,000Hz. This peak was interpreted as the second resonance of the epilarynx tube. Singers in other voice categories who produce vocal ring are assumed to have the same peak, but no measurements have as yet been made. Materials and Methods : Fifteen tenors, fourteen baritones, seven sopranos and five mezzo sopranos attending the music college, department of vocal music who could reliably produce the head and chest registers were chosen for this study. Each subject was asked to produce an/ah/sound for at least three seconds for the head register sound(tenors ; G4, barions ; E4 sopranos ; F5 and mezzosopranos ; C5) and for the chest register sound (tenors ; C3, baritones ; D3, sopranos ; D4 and Mezzosoprano ; A3). The sound data was analyzed using the Fast Fourier Transform (FFT)-based power spectrum, Long term average(LTA) power spectrum using the FFT algorithm of the Computerized Speech Lab (CSL, Kay elemetrics, Model 4300B, USA). Statistical analysis was performed using the Mann-Whitney test of the Statistical Package for Social sciences(SPSS). Results : For head register sounds, a significant increase was seen in the 2,200-3,400Hz region(p<0.05) and the Similar to the head register sounds, there was a significant increase in energy in the four trained singer group compared with the untrained group in the 2,200-3,100Hz region(p<0.05), the 7,800-8,400Hz region(p<0.05) for the chest register sounds. Conclusions : When good vocal production was made for the head and chest registers, an energy peak was observed near 2,500Hz, a frequency already known as the "singer's formant', in all subjects in the study group. Another region of increased energy was observed around 8,000Hz that had not been noticed previously. The authors believe this region to be the second singer's formant.

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Clinical Study of Surgical Treatment of Acquired Tricuspid Regurgitation (후천성 삼첨판폐쇄부전증의 외과적 치료에 대한 연구)

  • Lee, Hyeong-Ryeol;Kim, Jong-Won
    • Journal of Chest Surgery
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    • v.26 no.3
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    • pp.196-203
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    • 1993
  • Fourty-five cases of operation were performed for the correction of tricuspid regurgitation [TR] in Pusan National University Hospital between 1982 and 1991.The mean age of the patients was 32.6 years and female was dominant[M:F=1:2.2].Isolated tricuspid regurgitation was rare and 43 patients underwent concomitant other valvular operation including mitral valve replacement. Functional cause was in 39 cases and organic lesions were found in 6 cases. Operative methods were Kay annuloplasty[29], De Vega annuloplasty[12], and tricuspid valve replacement[4]. Ring annuloplasty was not performed. Operative mortality rate was 11.1%[5/45] and late mortality rate was 6.7%[2/30]. The tricuspid valve surgery itself was not a serious risk factor for hospital death and no heart block nor thrombosis was complicated. By echocardiogram early[within 30 days] and late [mean:4.9years] changes of postoperative TR were evaluated. De Vega annuloplasty seemed to bring better late result than Kay annuloplasty[p<0.05]. In four patients with late severe TR,previously replaced tissue valve degeneration[2], pulmonary hypertension[1] and rheumatic TR[1] were the possible causes. This experience suggests that De Vega annuloplasty can be a reliable method in the majority of patients with moderate-to-severe functional TR.

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The Solvent-Independent Structure of Piroxicam (피록시캄의 용매 비의존 결정구조)

  • Kim, Bong-Hee;Suh, Il-Hwan;Jhee, Ok-In;Suh, Jong-Myung;Suh, Jung-Jin
    • Journal of Pharmaceutical Investigation
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    • v.18 no.4
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    • pp.209-215
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    • 1988
  • The three-dimensional structures of piroxicam crystallized from two different solvents, toluene and toluene/hexane mixture respectively, are proved identical: $C_{15}H_{13}N_3O_4S,\;M\;=\;331.35$, monoclinic, a = 7.128(1), b = 15.146(2), c = 13.956(2) ${\AA},\;{\beta}=\;97.33(1)^{\circ},\;V\;=\;1494.37{\AA}^{3},\;Dx\;=\;1.472\;g/cm^{3},\;Z\;=\;4,\;space\;group\;P2_{1}/c,\;Mo\;K{\alpha}(\lambda=\;0.71073\;{\AA})$, F(000) = 688, T = 295 K, R = 0.0611 for 1993 unique observed reflections. The thiazine ring exhibits a half chair conformation. An amide group is involved in an intramolecular hydrogen bond to the hydroxy group, O(17)-H(17)${\cdots}O(15){\AA}$. The molecule is planar within 2 ${\AA}$ with the interplanar angle $127.9(4)^{\circ}$ between pyridine and benzene rings. A molecular chain parallel to [011] is formed by two intermolecular hydrogen bonds N(16)-H(6)${\cdots}O(11)$ and C(6)-H(6)${\cdots}O(11)$, and the molecular chains are held together by van der Waals forces.

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