• Title/Summary/Keyword: chemical states

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The Mechanism of the Photocyclization of N-(2-Haloarylmethyl)Pyridinium and N-(arylmethyl)-2-Halopyridinium Salts

  • Yong-Tae Park;Chang-Han Joo;Chung-Do Choi;Kum-Soo Park
    • Bulletin of the Korean Chemical Society
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    • v.12 no.2
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    • pp.163-169
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    • 1991
  • The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.

Analysis of Chemical Compounds of Gaseous and Particulate Pollutants from the Open Burning of Agricultural HDPE Film Waste

  • Kim, Tae-Han;Choi, Boo-Hun;Kook, Joongjin
    • Journal of People, Plants, and Environment
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    • v.24 no.6
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    • pp.585-593
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    • 2021
  • Background and objective: Illegal open-air incineration, which is criticized as a leading source of air pollutants among agricultural activities, currently requires constant effort and attention. Countries around the world have been undertaking studies on the emission of heavy metal substances in fine dust discharged during the incineration process. A precise analytical method is required to examine the harmful effects of particulate pollutants on the human body. Methods: In order to simulate open-air incineration, the infrastructure needed for incineration tests complying with the United States Environmental Protection Agency (EPA) Method 5G was built, and a large-area analysis was conducted on particulate pollutants through automated scanning electron microscopy (SEM)-energy-dispersive X-ray spectroscopy (EDS). For the test specimen, high-density polyethylene (HDPE) waste collected by the DangJin Office located in Choongcheongnam-do was used. To increase the identifiability of the analyzed particles, the incineration experiment was conducted in an incinerator three times after dividing the film waste into 200 g specimens. Results: Among the metal particulate matters detected in the HDPE waste incineration test, transition metals included C (20.8-37.1 wt%) and O (33.7-37.9 wt%). As for other chemical matters, the analysis showed that metal particulate matters such as metalloids, alkali metals, alkaline earth metals, and transition metals reacted to C and C-O. Si, a representative metalloid, was detected at 14.8-20.8 wt%, showing the highest weight ratio except for C and O. Conclusion: In this study, the detection of metal chemicals in incinerated particulate matters was effectively confirmed through SEM-EDS. The results of this study verified that HDPE waste adsorbs metal chemicals originating from soil due to its own properties and deterioration, and that when incinerated, it emits particulate matters containing transition metals and other metals that contribute to the excessive production and reduction of reactive oxygen species.

Comparison of Chemical Composition of Particulate Matter Emitted from a Gasoline Direct Injected (GDI) Vehicle and a Port Fuel Injected (PFI) Vehicle using High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS)

  • Lee, Jong Tae;Son, Jihwan;Kim, Jounghwa;Choi, Yongjoo;Yoo, Heung-Min;Kim, Ki Joon;Kim, Jeong Soo;Park, Sung Wook;Park, Gyutae;Park, Taehyun;Kang, Seokwon;Lee, Taehyoung
    • Asian Journal of Atmospheric Environment
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    • v.10 no.1
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    • pp.51-56
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    • 2016
  • Particulate matter (PM) in the atmosphere has wide-ranging health, environmental, and climate effects, many of which are attributed to fine-mode secondary organic aerosols. PM concentrations are significantly enhanced by primary particle emissions from traffic sources. Recently, in order to reduce $CO_2$ and increase fuel economy, gasoline direct injected (GDI) engine technology is increasingly used in vehicle manufactures. The popularization of GDI technique has resulted in increasing of concerns on environmental protection. In order to better understand variations in chemical composition of particulate matter from emissions of GDI vehicle versus a port fuel injected (PFI) vehicle, a high time resolution chemical composition of PM emissions from GDI and PFI vehicles was measured at facility of Transport Pollution Research Center (TPRC), National Institute of Environmental Research (NIER), Korea. Continuous measurements of inorganic and organic species in PM were conducted using an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The HR-ToF-AMS provides insight into non-refractory PM composition, including concentrations of nitrate, sulfate, hydrocarbon-like and oxygenated organic aerosol, and organic mass with 20 sec time resolution. Many cases of PM emissions during the study were dominated by organic and nitrate aerosol. An overview of observed PM characteristics will be provided along with an analysis of comparison of GDI vehicle versus PFI vehicle in PM emission rates and oxidation states.

The Distribution Characteristics of Grain Size and Organic Matters of Surface Sediments from the Nakdong-Goryeong Mid-watershed (낙동·고령 중권역의 표층 퇴적물 입도 조성 및 유기물질 분포 특성 변화)

  • Kim, Shin;Ahn, Jungmin;Kim, Hyounggeun;Kwon, Heongak;Kim, Gyeonghoon;Shin, Dongseok;Yang, Deukseok
    • Journal of Environmental Science International
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    • v.27 no.6
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    • pp.411-423
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    • 2018
  • To investigate the distribution characteristics of grain size and organic matter of surface sediments from the Nakdong-Goryeong Mid-watershed, surface sediments were collected and analyzed. The samples were collected from six sited at four different times between May 2013 and May 2014. The were analyzed for grain size, water content, ignition loss, chemical oxygen demand, total organic carbon and total nitrogen. The surface sediments were mainly composed of medium sand (mean 44.7%) and coarse sand (mean 32.8%) and became coarser in May 2014. Fine sediments at the site NG-2 were poorly sorted and positively skewed, and occur in a tributary environment that is relatively low-energy compared with the other sites. The water content at the studied sites (15.3 ~ 34.9%) averaged 20.25%, and ignition loss (0.4 ~ 5.8%) and total nitrogen (274 ~ 2493 mg/kg) averaged 1.33% and, 696 mg/kg, respectively. These values indicated that the sediments were not seriously contaminated when compared with the sediment pollution evaluation standard of the National Institute of Environmental Research. The chemical oxygen demand (mean 0.17%) was at the non-polluted level compared with United States Environmental Protection Agency sediment quality standards. The total organic carbon (mean 0.18%) at all sites except site NG-2 (lowest effect level) was the no effect level of the Ontario sediment quality guidelines. The COD/IL (0.02 ~ 0.20) and C/N (0.73 ~ 6.76) were less than 1 and 10, respectively. Organic matter in the study area produced naturally from aquatic organisms. Results of principal component analysis showed that fine sediments (very fine sand and silt) were significantly affected by organic matters (ignition loss, chemical oxygen demand, total organic carbon and total nitrogen). In addition, the highest organic matters content in the study area occurred at the site with the finest sediments (NG-2).

Production and Analysis of Oxygenated Unsaturated Fatty Acids from Oleic Acid by Flavobacterium sp. Strain DS5 (Flavobacterium sp. Strain DS5에 의한 Oleic Acid로부터 산화불포화 지방산의 생산 및 분석)

  • Song, Byung-Seob;Han, Nam-Soo;Lee, Bong-Hee;Hou, Ching T.;Kim, Beom-Soo
    • KSBB Journal
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    • v.24 no.1
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    • pp.41-46
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    • 2009
  • Vegetable oils are desirable inexpensive feedstocks for various bioproducts. The content of unsaturated fatty acids such as oleic and linoleic acids are 22% and 55% for soybean oil, 26% and 60% for corn oil, and 61% and 21% for canola oil, respectively. Keto and hydroxy fatty acids are useful industrial chemicals, used in plasticizer, surfactant, lubricant and detergent formulations because of their special chemical properties such as higher viscosity and reactivity compared with other fatty acids. In this study, a microbial isolate, Flavobacterium sp. strain DS5 (NRRL B-14859), was used to convert oleic acid to 10-ketostearic acid (10-KSA) via 10-hydroxystearic acid (10-HSA). Two bioconversion products, 10-KSA and 10-HSA, were quantitatively and qualitatively analyzed using gas chromatography, gas chromatography-mass spectrometry, and $^1H-$ and $^{13}C$-nuclear magnetic resonance. The maximum production of 10-KSA and 10-HSA in flask cultures were 3.4 g/L and 0.5 g/L, respectively. The optimum concentrations of glucose and yeast extract, addition time and volume of oleic acid for 10-KSA production were less than 20 g/L, more than 5 g/L, 18 hand 0.3 ml/50 ml, respectively.

(Photosensitive Polymers VII) Mechanism of Photosensitized Curing Reaction of Cinnamoylated Polymers ((感光性 高分子에 關한 硏究 VII) Cinnamoylated Polymers의 光增感 硬化反應機構)

  • Kim, Kwang-Sup;Shim, Jyong-Sup
    • Journal of the Korean Chemical Society
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    • v.10 no.4
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    • pp.166-174
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    • 1966
  • The multistep mechanism of photosensitized curing reaction cinnamoylated photosensitive polymer is proposed from the energy level diagram of cinnamic acid and sensitizer, and from the fact that excess of sensitizer brings the sensitivity to a limiting value etc. Various factors which have effects on the ability of sensitizer are also discussed. The mechanism involves following steps: activation to the first excited singlet states of cinnamoyl group(C) and sensitizer(S) by their absorption of photon, their intersystem crossing to the lowest triplet state, bimolecular internal quenching by formation of excimer of sensitizer, triplet excitation energy transfer and intermolecular addition between cinnamoyl group in ground state and that in triplet state. The rate equation derived from this mechanism is $-\frac{d[C]}{dt} = \frac{K_1[C]}{K_2 + [C]}[\frac{I^c_{abs}}{K_3 + [S]} + \frac{K_4[C]}{(K_5 + [C])(K_6 + [S])}(I^s_{abs} + \frac{K_7I^c_{abs}[S]}{K_8 + [S]})]$ where $I^c_{abs}\;and\;I^s_{abs}$: the rates of absorption of photon by cinnamoyl group and sensitizer $K_n$: Constants. It is proved with the cinnamate of poly(glyceryl phthalate)(PGC) in the absence of sensitizer using the infrared analytical method and successfully applied for the experimental data reported on the effects of the degree of cinnamoyl esterification and the concentration of sensitizer upon the sensitivity.

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Review of Problems with Use of Halogenated Cleaning Solvents Revealed through Case Studies of Cleaning Solvent Poisoning and Analysis of Domestic and Overseas Regulations (세척제 용매 중독 사례와 국내·외 규제 검토를 통한 할로겐화 용매 세척제 사용의 문제점 고찰)

  • Naroo Lee;Hye Jin Lee;Sujin Jeong;Dohee Lee;Arom Shin
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.33 no.4
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    • pp.517-527
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    • 2023
  • Objectives: We examine cases of chemical poisoning that occurred in the cleaning of metal parts and the regulations on halogenated solvents in other countries and propose regulations necessary to prevent chemical poisoning from halogenated solvents. Methods: We collected cases of chemical poisoning through the website of the Korea Occupational Safety and Health Agency. A review of the literature was conducted focusing on regulations related to halogenated solvents in the United States and the European Union, particularly for cleaning metal parts. Among the Material Safety Data Sheets submitted to the government, MSDS containing eleven substances were extracted to confirm the composition and product use. We investigated cleaning methods for metal parts used in South Korea. For the hazard classification, the European Chemicals Agency or Japan's NITE's website was used. Results: In the case of poisoning, the cleaning methods involving trichloromethane were dipping and dry, which was not found in the literature. It was confirmed that many halogenated solvents and dimethyl carbonate were used for metal cleaning in South Korea. In vapor degreasing using TCE in the USA, even if the facility is strictly managed, such as by installing cooling coils in open cleaning facilities, the risk of exposure to TCE is considered to be not only carcinogenic but also a concern for acute and chronic effects. In comparison, exposure through Korean work methods such as dipping and drying operations is inevitably much higher. Conclusions: The transition to water-based cleaning with low-hazard chemicals should be a priority in the cleaning process. In the case of metal parts that require precise cleaning, if the use of a halogenated solvent is inevitable, a closed degreasing facility should be used to minimize exposure. The current regulations in the Occupational Safety and Health Act, the Chemical Substances Control Act, and the Air Environment Conservation Act do not require cleaning facilities to minimize emissions. To protect the health of workers using halogenated solvents to clean metal parts, regulations that require a fundamental reduction in exposure will be necessary.

Added Value of Chemical Exchange-Dependent Saturation Transfer MRI for the Diagnosis of Dementia

  • Jang-Hoon Oh;Bo Guem Choi;Hak Young Rhee;Jin San Lee;Kyung Mi Lee;Soonchan Park;Ah Rang Cho;Chang-Woo Ryu;Key Chung Park;Eui Jong Kim;Geon-Ho Jahng
    • Korean Journal of Radiology
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    • v.22 no.5
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    • pp.770-781
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    • 2021
  • Objective: Chemical exchange-dependent saturation transfer (CEST) MRI is sensitive for detecting solid-like proteins and may detect changes in the levels of mobile proteins and peptides in tissues. The objective of this study was to evaluate the characteristics of chemical exchange proton pools using the CEST MRI technique in patients with dementia. Materials and Methods: Our institutional review board approved this cross-sectional prospective study and informed consent was obtained from all participants. This study included 41 subjects (19 with dementia and 22 without dementia). Complete CEST data of the brain were obtained using a three-dimensional gradient and spin-echo sequence to map CEST indices, such as amide, amine, hydroxyl, and magnetization transfer ratio asymmetry (MTRasym) values, using six-pool Lorentzian fitting. Statistical analyses of CEST indices were performed to evaluate group comparisons, their correlations with gray matter volume (GMV) and Mini-Mental State Examination (MMSE) scores, and receiver operating characteristic (ROC) curves. Results: Amine signals (0.029 for non-dementia, 0.046 for dementia, p = 0.011 at hippocampus) and MTRasym values at 3 ppm (0.748 for non-dementia, 1.138 for dementia, p = 0.022 at hippocampus), and 3.5 ppm (0.463 for non-dementia, 0.875 for dementia, p = 0.029 at hippocampus) were significantly higher in the dementia group than in the non-dementia group. Most CEST indices were not significantly correlated with GMV; however, except amide, most indices were significantly correlated with the MMSE scores. The classification power of most CEST indices was lower than that of GMV but adding one of the CEST indices in GMV improved the classification between the subject groups. The largest improvement was seen in the MTRasym values at 2 ppm in the anterior cingulate (area under the ROC curve = 0.981), with a sensitivity of 100 and a specificity of 90.91. Conclusion: CEST MRI potentially allows noninvasive image alterations in the Alzheimer's disease brain without injecting isotopes for monitoring different disease states and may provide a new imaging biomarker in the future.

The Study of the Etch Characteristics of the TaN Thin Film Using an Inductively Coupled Plasma (유도 결합 플라즈마를 이용한 TaN 박막의 건식 식각 특성 연구)

  • Um, Doo-Seung;Kim, Seung-Han;Woo, Jong-Chang;Kim, Chang-Il
    • Journal of the Korean institute of surface engineering
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    • v.42 no.6
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    • pp.251-255
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    • 2009
  • In this study, the plasma etching of the TaN thin film with $O_2/BCl_3$/Ar gas chemistries was investigated. The equipment for the etching was an inductively coupled plasma (ICP) system. The etch rate of the TaN thin film and the selectivity of TaN to $SiO_2$ and PR was studied as a function of the process parameters, including the amount of $O_2$ added, an RF power, a DC-bias voltage and the process pressure. When the gas mixing ratio was $O_2$(3 sccm)/$BCl_3$(6 sccm)/Ar(14 sccm), with the other conditions fixed, the highest etch rate was obtained. As the RF power and the dc-bias voltage were increased, the etch rate of the TaN thin film was increased. X-ray photoelectron spectroscopy (XPS) was used to investigate the chemical states of the surface of the TaN thin film.

Analysis of Interfaces and Structures of DLC Films Deposited by FCVA Method (FCVA 방법으로 증착된 DLC 박막의 계면 및 구조분석)

  • Park, Chang-Kyun;Chang, Seok-Mo;Uhm, Hyun-Seok;Seo, Soo-Hyung;Park, Jin-Seok
    • Proceedings of the KIEE Conference
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    • 2001.11a
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    • pp.16-19
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    • 2001
  • DLC films are deposited using a modified FCVA system. Carbon amorphous networks, chemical bonding states, $sp^3$ fraction, interfaces, and structures are studied as a function of substrate voltage ($0{\sim}-250V$). The $sp^3$ content in the films is evaluated by analyzing the XPS spectra(C1s). The structural properties of the surface, bulk, and interfacial layers in DLC/Si systems are quantitatively analyzed by employing XRR method. As the substrate voltage is increased, the $sp^3$ fraction is decreased by means of XPS and Raman spectroscopy. In addition, the structural properties (interfacial layer, contamination layer, and sp3 fraction) derived from XPS depth profile are relatively correlated with the XRR results.

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