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Performance of Korean State-owned Enterprises Following Executive Turnover and Executive Resignation During the Term of Office (공기업의 임원교체와 중도퇴임이 경영성과에 미치는 영향)

  • Yu, Seungwon;Kim, Suhee
    • KDI Journal of Economic Policy
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    • v.34 no.3
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    • pp.95-131
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    • 2012
  • This study examines whether the executive turnover and the executive resignation during the term of office affect the performance of Korean state-owned enterprises. The executive turnover in the paper means the comprehensive change of the executives which includes the change after the term of office, the change after consecutive terms and the change during the term of office. The 'resignation' was named for the executive change during the term of office to distinguish from the executive turnover. The study scope of the paper is restrained to the comprehensive executive change itself irrespective of the term of office and the resignation during the term of office. Therefore the natural change of the executive after the term of office or the change after consecutive terms is not included in the study. Spontaneous resignation and forced resignation are not distinguished in the paper as the distinction between the two is not easy. The paper uses both the margin of return on asset and the margin of return on asset adjusted by industry as proxies of the performance of state-owned enterprises. The business nature of state-owned enterprise is considered in the study, the public nature not in it. The paper uses the five year (2004 to 2008) samples of 24 firms designated as public enterprises by Korean government. The analysis results are as follows. First, 45.1% of CEOs were changed a year during the sample period on the average. The average tenure period of CEOs was 2 years and 3 months and 49.9% among the changed CEOs resigned during the term of office. 41.6% of internal auditors were changed a year on the average. The average tenure period of internal auditors was 2 years and 2 months and 51.0% among the changed internal auditors resigned during the term of office. In case of outside directors, on average, 38.2% were changed a year. The average tenure period was 2 years and 7 months and 25.4% among the changed internal directors resigned during the term of office. These statistics show that numerous CEOs resigned before the finish of the three year term in office. Also, considering the tenure of an internal auditor and an outside director which diminished from 3 years to 2 years by an Act on the Management of Public Institutions (applied to the executives appointed since April 2007), it seems most internal auditors resigned during the term of office but most outside directors resigned after the end of the term. Secondly, There was no evidence that the executives were changed during the term of office because of the bad performance of prior year. On the other hand, contrary to the normal expectation, the performance of prior year of the state-owned enterprise where an outside director resigned during the term of office was significantly higher than that of other state-owned enterprises. It means that the clauses in related laws on the executive dismissal on grounds of bad performance did not work normally. Instead it can be said that the executive change was made by non-economic reasons such as a political motivation. Thirdly, the results from a fixed effect model show there were evidences that performance turned negatively when CEOs or outside directors resigned during the term of office. CEO's resignation during the term of office gave a significantly negative effect on the margin of return on asset. Outside director's resignation during the term of office lowered significantly the margin of return on asset adjusted by industry. These results suggest that the executive's change in Korean state-owned enterprises was not made by objective or economic standards such as management performance assessment and the negative effect on performance of the enterprises was had by the unfaithful obeyance of the legal executive term.

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Genetic Counseling in Korean Health Care System (한국 의료제도와 유전상담 서비스의 구축)

  • Kim, Hyon-J.
    • Journal of Genetic Medicine
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    • v.8 no.2
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    • pp.89-99
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    • 2011
  • Over the years Korean health care system has improved in delivery of quality care to the general population for many areas of the health problems. The system is now being recognized in the world as the most cost effective one. It is covered by the uniform national health insurance policy for which most people in Korea are mandatory policy holders. Genetic counseling service, however, which is well recognized as an integral part of clinical genetics service deals with diagnosis and management of genetic condition as well as genetic information presentation and family support, is yet to be delivered in comprehensive way for the patients and families in need. Two major obstacles in providing genetic counseling service in korean health care system are identified; One is the lack of recognition for the need for genetic counseling service as necessary service by the national health insurance. Genetic counseling consumes a significant time in delivery and the current very low-fee schedule for physician service makes it very difficult to provide meaningful service. Second is the critical shortage of qualified professionals in the field of medical genetics and genetic counseling who can provide the service of genetic counseling in clinical setting. However, recognition and understanding of the fact that the scope and role of genetic counseling is expanding in post genomic era of personalized medicine for delivery of quality health care, will lead to the efforts to overcome obstacles in providing genetic counseling service in korean health care system. Only concerted efforts from health care policy makers of government on clinical genetics service and genetic counseling for establishing adequate reimbursement coverage and professional communities for developing educational program and certification process for professional genetic counselors, are necessary for the delivery of much needed clinical genetic counseling service in Korea.

Legal Study for the KSLV launching - Products & Third Party Liability - (KSLV발사에 따른 제작 및 제3자피해 책임에 대한 우주법적 소고)

  • Shin, Sung-Hwan
    • The Korean Journal of Air & Space Law and Policy
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    • v.21 no.1
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    • pp.169-189
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    • 2006
  • In 2007, KSLV(Korea Small Launching Vehicle) that we made at Goheung National Space Center is going to launch and promotes of our space exploration systematically and 'Space Exploration Promotion Act' was enter into force. 'Space Exploration Promotion Act' article 3, section 1, as is prescribing "Korean government keeps the space treaties contracted with other countries and international organizations and pursues after peaceful uses of outer space." The representative international treaties are Outer Space Treaty (1967) and Liability Convention (1972) etc. In Liability convention article 2, "A launching State shall be absolutely liable to pay compensation for damage caused by its space object on the surface of the earth or to aircraft in flight. The important content of the art. 2 is the responsible entity is the 'State' not the 'Company'. According by Korean Space Exploration Act art. 14, person who launches space objects according to art. 8 and art. 11 must bear the liability for damages owing to space accidents of the space objects. Could Korean government apply the Products Liability Act which is enter into force from July 1, 2002 to space launching person? And what is the contact type between Korea Aerospace Research Institute(KARl) and Russia manufacturer. Is that a Co-Development contract or Licence Product contract? And there is no exemption clause to waive the Russia manufacturer's liability which we could find it from other similar contract condition. If there is no exemption clause to the Russia manufacturer, could we apply the Korean Products Liability Act to Russia one? The most important legal point is whether we could apply the Korean Products Liability Act to the main component company. According by the art. 17 of the contract between KARl and the company, KARl already apply the Products Liability Act to the main component company. For reference, we need to examine the Appalachian Insurance co. v. McDonnell Douglas case, this case is that long distance electricity communication satellite of Western Union Telegraph company possessions fails on track entry. In Western Union's insurance company supplied to Western Union with insurance of $ 105 millions, which has the satellite regard as entirely damage. Five insurance companies -Appalachian insurance company, Commonwealth insurance company, Industrial Indemnity, Mutual Marine Office, Northbrook Excess & Surplus insurance company- went to court against McDonnell Douglases, Morton Thiokol and Hitco company to inquire for fault and strict liability of product. By the Appalachian Insurance co. v. McDonnell Douglas case, KARl should waiver the main component's product liability burden. And we could study the possibility of the adapt 'Government Contractor Defense' theory to the main component company.

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Conclusion of Conventions on Compensation for Damage Caused by Aircraft in Flight to Third Parties (항공운항 시 제3자 피해 배상 관련 협약 채택 -그 혁신적 내용과 배경 고찰-)

  • Park, Won-Hwa
    • The Korean Journal of Air & Space Law and Policy
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    • v.24 no.1
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    • pp.35-58
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    • 2009
  • A treaty that governs the compensation on damage caused by aircraft to the third parties on surface was first adopted in Rome in 1933, but without support from the international aviation community it was replaced by another convention adopted again in Rome in 1952. Despite the increase of the compensation amount and some improvements to the old version, the Rome Convention 1952 with 49 State parties as of today is not considered universally accepted. Neither is the Montreal Protocol 1978 amending the Rome Convention 1952, with only 12 State parties excluding major aviation powers like USA, Japan, UK, and Germany. Consequently, it is mostly the local laws that apply to the compensation case of surface damage caused by the aircraft, contrary to the intention of those countries and people who involved themselves in the drafting of the early conventions on surface damage. The terrorist attacks 9/11 proved that even the strongest power in the world like the USA cannot with ease bear all the damages done to the third parties by the terrorist acts involving aircraft. Accordingly as a matter of urgency, the International Civil Aviation Organization(ICAO) picked up the matter and have it considered among member States for a few years through its Legal Committee before proposing for adoption as a new treaty in the Diplomatic Conference held in Montreal, Canada 20 April to 2 May 2009. Accordingly, two treaties based on the drafts of the Legal Committee were adopted in Montreal by consensus, one on the compensation for general risk damage caused by aircraft, the other one on compensation for damage from acts of unlawful interference involving aircraft. Both Conventions improved the old Convention/Protocol in many aspects. Deleting 'surface' in defining the damage to the third parties in the title and contents of the Conventions is the first improvement because the third party damage is not necessarily limited to surface on the soil and sea of the Earth. Thus Mid-air collision is now the new scope of application. Increasing compensation limit in big gallop is another improvement, so is the inclusion of the mental injury accompanied by bodily injury as the damage to be compensated. In fact, jurisprudence in recent years for cases of passengers in aircraft accident holds aircraft operators to be liable to such mental injuries. However, "Terror Convention" involving unlawful interference of aircraft has some unique provisions of innovation and others. While establishing the International Civil Aviation Compensation Fund to supplement, when necessary, the damages that exceed the limit to be covered by aircraft operators through insurance taking is an innovation, leaving the fate of the Convention to a State Party, implying in fact the USA, is harming its universality. Furthermore, taking into account the fact that the damage incurred by the terrorist acts, where ever it takes place targeting whichever sector or industry, are the domain of the State responsibility, imposing the burden of compensation resulting from terrorist acts in the air industry on the aircraft operators and passengers/shippers is a source of serious concern for the prospect of the Convention. This is more so when the risks of terrorist acts normally aimed at a few countries because of current international political situation are spread out to many innocent countries without quid pro quo.

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The Current Status of the Discussions on International Norms Related to Space Activities in the UN COPUOS Legal Subcommittee (우주활동 국제규범에 관한 유엔 우주평화적이용위원회 법률소위원회의 최근 논의 현황)

  • Jung, Yung-Jin
    • The Korean Journal of Air & Space Law and Policy
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    • v.29 no.1
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    • pp.127-160
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    • 2014
  • The UN COPUOS was established in 1959 as a permanent committee of the UN General Assembly with the aims to promote international cooperation in peaceful uses of outer space, to formulate space-related programmes within the UN, to encourage research and dissemination of information on space, and to study legal problems arising from the outer space activities. Its members have been enlarged from 24 members in 1959 to 76 in 2014. The Legal Subcommittee, which has been established under COPUOS in 1962 to deal with legal problems associated with space activities, through its first three decades of work has set up a framework of international space law: the five treaties and agreements - namely the Outer Space Treaty, Rescue Agreement, Liability Convention, Registration Convention, Moon Agreement - and the five declarations and legal principles. However, some sceptical views on this legal framework has been expressed, concerning the applicability of existing international space law to practical issues and new kinds of emerging space activities. UNISPACE III, which took place in 1999, served as a momentum to revitalize the discussions of the legal issues faced by the international community in outer space activities. The agenda of the Legal Subcommittee is currently structured into three categories: regular items, single issue/items, and items considered under a multi-year workplan. The regular items, which deal with basic legal issues, include definition and delimitation of outer space, status and application of the five UN treaties on outer space, and national legislation relevant to the peaceful exploration and use of outer space. The single issues/items, which are decided upon the preceding year, are discussed only for one year in the plenary unless renewed. They include items related to the use of nuclear power sources in outer space and to the space debris mitigation. The agenda items considered under a multi-year work plan are discussed in working group. Items under this category deal with non-legally binding UN instruments on outer space and international mechanism for cooperation. In recent years, the Subcommittee has made some progress on agenda items related to nuclear power sources, space debris, and international cooperation by means of establishing non-legally binding instruments, or soft law. The Republic of Korea became the member state of COPUOS in 2001, after rotating seats every two years with Cuba and Peru since 1994. Korea's joining of COPUOS seems to be late, in considering that some countries with hardly any space activity, such Chad, Sierra Leone, Kenya, Lebanon, Cameroon, joined COPUOS as early as 1960s and 1970s and contributed to the drafting of the aforementioned treaties, declarations, and legal principles. Given the difficulties to conclude a treaty and un urgency to regulate newly emerging space activities, Legal Subcommittee now focuses its effort on developing soft law such as resolutions and guideline to be adopted by UN General Assembly. In order to have its own practices reflected in the international practices, one of the constituent elements of international customary law, Korea should analyse its technical capability, policy, and law related to outer space activities and participate actively in the formation process of the soft law.

A Study on Aviation Safety and Third Country Operator of EU Regulation in light of the Convention on international Civil Aviation (시카고협약체계에서의 EU의 항공법규체계 연구 - TCO 규정을 중심으로 -)

  • Lee, Koo-Hee
    • The Korean Journal of Air & Space Law and Policy
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    • v.29 no.1
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    • pp.67-95
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    • 2014
  • Some Contracting States of the Chicago Convention issue FAOC(Foreign Air Operator Certificate) and conduct various safety assessments for the safety of the foreign operators which operate to their state. These FAOC and safety audits on the foreign operators are being expanded to other parts of the world. While this trend is the strengthening measure of aviation safety resulting in the reduction of aircraft accident. FAOC also burdens the other contracting States to the Chicago Convention due to additional requirements and late permission. EASA(European Aviation Safety Agency) is a body governed by European Basic Regulation. EASA was set up in 2003 and conduct specific regulatory and executive tasks in the field of civil aviation safety and environmental protection. EASA's mission is to promote the highest common standards of safety and environmental protection in civil aviation. The task of the EASA has been expanded from airworthiness to air operations and currently includes the rulemaking and standardization of airworthiness, air crew, air operations, TCO, ATM/ANS safety oversight, aerodromes, etc. According to Implementing Rule, Commission Regulation(EU) No 452/2014, EASA has the mandate to issue safety authorizations to commercial air carriers from outside the EU as from 26 May 2014. Third country operators (TCO) flying to any of the 28 EU Member States and/or to 4 EFTA States (Iceland, Norway, Liechtenstein, Switzerland) must apply to EASA for a so called TCO authorization. EASA will only take over the safety-related part of foreign operator assessment. Operating permits will continue to be issued by the national authorities. A 30-month transition period ensures smooth implementation without interrupting international air operations of foreign air carriers to the EU/EASA. Operators who are currently flying to Europe can continue to do so, but must submit an application for a TCO authorization before 26 November 2014. After the transition period, which lasts until 26 November 2016, a valid TCO authorization will be a mandatory prerequisite, in the absence of which an operating permit cannot be issued by a Member State. The European TCO authorization regime does not differentiate between scheduled and non-scheduled commercial air transport operations in principle. All TCO with commercial air transport need to apply for a TCO authorization. Operators with a potential need of operating to the EU at some time in the near future are advised to apply for a TCO authorization in due course, even when the date of operations is unknown. For all the issue mentioned above, I have studied the function of EASA and EU Regulation including TCO Implementing Rule newly introduced, and suggested some proposals. I hope that this paper is 1) to help preparation of TCO authorization, 2) to help understanding about the international issue, 3) to help the improvement of korean aviation regulations and government organizations, 4) to help compliance with international standards and to contribute to the promotion of aviation safety, in addition.

A Study on Developing a VKOSPI Forecasting Model via GARCH Class Models for Intelligent Volatility Trading Systems (지능형 변동성트레이딩시스템개발을 위한 GARCH 모형을 통한 VKOSPI 예측모형 개발에 관한 연구)

  • Kim, Sun-Woong
    • Journal of Intelligence and Information Systems
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    • v.16 no.2
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    • pp.19-32
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    • 2010
  • Volatility plays a central role in both academic and practical applications, especially in pricing financial derivative products and trading volatility strategies. This study presents a novel mechanism based on generalized autoregressive conditional heteroskedasticity (GARCH) models that is able to enhance the performance of intelligent volatility trading systems by predicting Korean stock market volatility more accurately. In particular, we embedded the concept of the volatility asymmetry documented widely in the literature into our model. The newly developed Korean stock market volatility index of KOSPI 200, VKOSPI, is used as a volatility proxy. It is the price of a linear portfolio of the KOSPI 200 index options and measures the effect of the expectations of dealers and option traders on stock market volatility for 30 calendar days. The KOSPI 200 index options market started in 1997 and has become the most actively traded market in the world. Its trading volume is more than 10 million contracts a day and records the highest of all the stock index option markets. Therefore, analyzing the VKOSPI has great importance in understanding volatility inherent in option prices and can afford some trading ideas for futures and option dealers. Use of the VKOSPI as volatility proxy avoids statistical estimation problems associated with other measures of volatility since the VKOSPI is model-free expected volatility of market participants calculated directly from the transacted option prices. This study estimates the symmetric and asymmetric GARCH models for the KOSPI 200 index from January 2003 to December 2006 by the maximum likelihood procedure. Asymmetric GARCH models include GJR-GARCH model of Glosten, Jagannathan and Runke, exponential GARCH model of Nelson and power autoregressive conditional heteroskedasticity (ARCH) of Ding, Granger and Engle. Symmetric GARCH model indicates basic GARCH (1, 1). Tomorrow's forecasted value and change direction of stock market volatility are obtained by recursive GARCH specifications from January 2007 to December 2009 and are compared with the VKOSPI. Empirical results indicate that negative unanticipated returns increase volatility more than positive return shocks of equal magnitude decrease volatility, indicating the existence of volatility asymmetry in the Korean stock market. The point value and change direction of tomorrow VKOSPI are estimated and forecasted by GARCH models. Volatility trading system is developed using the forecasted change direction of the VKOSPI, that is, if tomorrow VKOSPI is expected to rise, a long straddle or strangle position is established. A short straddle or strangle position is taken if VKOSPI is expected to fall tomorrow. Total profit is calculated as the cumulative sum of the VKOSPI percentage change. If forecasted direction is correct, the absolute value of the VKOSPI percentage changes is added to trading profit. It is subtracted from the trading profit if forecasted direction is not correct. For the in-sample period, the power ARCH model best fits in a statistical metric, Mean Squared Prediction Error (MSPE), and the exponential GARCH model shows the highest Mean Correct Prediction (MCP). The power ARCH model best fits also for the out-of-sample period and provides the highest probability for the VKOSPI change direction tomorrow. Generally, the power ARCH model shows the best fit for the VKOSPI. All the GARCH models provide trading profits for volatility trading system and the exponential GARCH model shows the best performance, annual profit of 197.56%, during the in-sample period. The GARCH models present trading profits during the out-of-sample period except for the exponential GARCH model. During the out-of-sample period, the power ARCH model shows the largest annual trading profit of 38%. The volatility clustering and asymmetry found in this research are the reflection of volatility non-linearity. This further suggests that combining the asymmetric GARCH models and artificial neural networks can significantly enhance the performance of the suggested volatility trading system, since artificial neural networks have been shown to effectively model nonlinear relationships.

A Study on Drainage Facilities in Mountainous Urban Neighborhood Parks - The Cases of Baebongsan Park and Ogeum Park in Seoul - (산지형 도시근린공원의 배수시설 특성 - 서울시 배봉산공원과 오금공원을 사례로 -)

  • Lee, Sang-Suk
    • Journal of the Korean Institute of Landscape Architecture
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    • v.38 no.5
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    • pp.80-92
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    • 2010
  • The purpose of this study was to analyze drainage facilities in mountainous urban neigbborhood parks--Baebongsan Park and Ogeum Park--in Seoul. Based on an analysis of existing drainage facilities, the volume of storm water runoff (VSW), the runoff rate of open channels(ROC), and the detention capacity of open charmels(DCOC) by each drainage watershed, the coefficient of runoff rate(CROC) as evaluated to be relevant between VSW and ROC and the coefficient of the detention capacity of open channe1s(CDCOC) as evaluated with DCOC compared to VSW were estimated and analyzed by parks and by watersheds. The results are as follows: 1. The total drainage area of Baebongsan Park was 34.13ha including surface runoff area(15.05ha; 44.09%), open channel area(l4.60ha; 42.78%), and natural waterway area(4.48ha; 13.13%). The total drainage area of Ogeum Park was 20.39ha including open channel area (10.14ha; 49.73%), ridge-side gutter area(7.17ha; 35.16%), surface runoff area (2.52ha; 12.36%), and natural waterway area (0.56ha; 2.75%). In Baebongsan Park, the portion of surface runoff was comparatively higher while the portion of artificial drainage area was higber in Ogeum Park. 2. In Baebongsan Park drainage districts were largely divided: VSW was $7.28m^3/s$ in total(average $0.23m^3/s$). Comparatively, tbe VSW in Ogeum Park, including smaller drainage districts, was $4.37m^3/s$ in total(average $0.12m^3/s$). 3. The ROC of Baebmgsan Park was $11.58m^3/s$ in total(average $0.77m^3/s$) and the CROC was 5.26, while in Ogeum Park, the ROC was $15.40m^3/s$(average $0.34m^3/s$) and tbe CROC was 8.87 higher than that of Baebongsan Because the size and slope of the open channel in Baebongsan Park was higher, the average ROC was larger, while tbe CROC of Ogeum Park was higher than that of Baebongsan Park, for the VSW in Ogeum Park was comparatively lower. 4. The DCOC in Baebongsan Park was $554.54m^3$ and the average of CDCOC was 179.83. That of Ogeum Park was $717.74m^3$ and the average of the CDCOC was 339.69, meaning that the DCOC of Ogeum Park was so much higber that drainage facilities in Ogeum Park were built intensively. This study was focused m the capacity of the drainage facilities in mountainous urban neighborhood parks by using the CROC to evaluate relevance between VSW and ROC and the CDCOC to evaluate the DCOC as compared with VSW. The devised methodology and coefficient for evaluating drainage facilities in mountainous urban neighborhood parks may he universally applicable through additional study. Further study m sustainable urban drainage systems for retaining rainwater in a reservoir and for enhancing ecological value is required in the near future.

Solution Phase Photolyses of Substituted Diphenyl Ether Herbicides under Simulated Environmental Conditions (모조(模造) 환경조건하(環境條件下)에서의 치환(置換) Diphenyl Ether 제초제(除草劑)의 광분해(光分解)에 관(關)한 연구(硏究))

  • Lee, Jae-Koo
    • Applied Biological Chemistry
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    • v.17 no.3
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    • pp.149-176
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    • 1974
  • Eight substituted diphenyl ether herbicides and some of their photoproducts were studied in terms of solution phase photolysis under simulated environmental conditions by using a Rayonet photochemical reactor. The test compounds absorbed sufficient light energy at the wavelength of 300 nm to undergo various photoreactions. All the photoproducts were confirmed by means of tlc, glc, ir, ms, and/or nmr spectrometry. The results obtained are summarized as follows: Solution phase photolysis of C-6989: An exceedingly large amount of p-nitrophenol formed strongly indicates the readiness of the ether linkage cleavage of this compound as the main reaction in all solvents used. Photoreduction of nitro to amino group(s) and photooxidation of trifluoromethyl to carboxyl group were recognized as minor reactions. Aqueous photolysis of p-nitrophenol: Quinone(0.28%), hydroquinone (0.66%), and p-aminophenol (0.42%) were confirmed as photoproducts, in addition to a relatively small amount of an unknown compound. The mechanisms of formation of these products were proposed to be the nitro-nitrite rearrangement via $n{\rightarrow}{\pi}^*$ excitation and the photoreduction through hydrogen abstractions by radicals, respectively. Solution phase photolysis of Nitrofen: Photochemical reduction leading to the p-amino derivative was the main reaction in n-hexane. In aqueous solution, the photoreduction of nitro to amino group and hydroxylation predominated over the ether linkage cleavage. Nucleophilic displacement of the nitro group by hydroxide ion and replacement of chlorine substituents by hydroxyl group or, to a lesser extent, hydrogen were also observed as minor reactoins. Solution phase photolysis of MO-338: Photoreduction of the nitro to amino group was marked in the n-hexane solution photolysis. In the aqueous solution, photoreduction of the nitro substituent and hydroxylation were the main reactions with replacement of chlorine substituents by the hydroxyl group and hydrogen, and cleavage of the ether linkage as minor reactions. Photolyses of MC-4379, MC-3761, MC-5127, MC-6063, and MC-7181 in n-hexane and cyclohexane: Photoreduction of the nitro group leading to the corresponding amino derivative and replacement of one of the halogen substituents by hydrogen from the solvent used were the key reactions in each compound. Aqueous photolysis of MC-4379: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, hydroxylation, and replacement of the nitro by hydroxy group were prominent with photoreduction and dechlorination as minor reactions. Aqueous photolysis of MC-3761: Cleavage of the ether linkage, replacement of the carboxymethyl by hydroxyl group, and photoreduction followed by hydroxylation were the main reactions. Aqueous photolysis of MC-5127: Replacement of carboxyethyl by hydrogen was predominant with ether linkage cleavage, photoreduction, and dechlorination as minor reactions. It was obvious that the decarboxyethylation proceeded more readily than decarboxymethylation occurring in the other compounds. Aqueous photolysis of MC-6063: Cleavage of the ether linkage and photodechlorination were the main reactions. Aqueous photolysis of MC-7181: Replacement of the carboxymethyl group by hydrogen and monodechlorination were the remarkable reactions. Cleavage of the ether linkage and hydroxylation were thought to be the minor reactions. Aqueous photolysis of 3-carboxymethyl-4-nitrophenol: The photo-induced Fries rearrangement common to aromatic esters did not appear to occur in the carboxymethyl group of this type of compound. Conversion of nitro to nitroso group was the main reaction.

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Studies on the ${\beta}-Tyrosinase$ -Part 2. On the Synthesis of Halo-tyrosine by ${\beta}-Tyrosinase$- (${\beta}-Tyrosinase$에 관한 연구 -제2보 ${\beta}-Tyrosinase$에 의한 Halogen화(化) Tyrosine의 합성(合成)-)

  • Kim, Chan-Jo;Nagasawa, Toru;Tani, Yoshiki;Yamada, Hideaki
    • Applied Biological Chemistry
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    • v.22 no.4
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    • pp.198-209
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    • 1979
  • L-Tyrosine, 2-chloro-L-tyrosine, 2-bromo-L-tyrosine, and 2-iodo-L-tyrosine were synthesized by ${\beta}-tyrosinase$ obtained from cells of Escherichia intermedia A-21, through the reversal of the ${\alpha},{\beta}-elimination$ reaction, and their molecular structures were analyzed by element analysis, NMR spectroscopy, mass spectrometry and IR spectroscopy. Rates of synthesis and hydrolysis of halogenated tyrosines by ${\beta}-tyrosinase$, inhibition of the enzyme activity by halogenated phenols, and effects of addition of m-bromophenol on the synthesis of 2-bromotyrosine were determined. The results obtained were as follows: 1) In the synthesis of halogenated tyrosines, the yield of 2-chlorotyrosine from m-chlorophenol were approximately 15 per cent, that of 2-bromotyrosine from m-bromophenol 13.8 per cent, and that of 2-iodotyrosine from m-iodophenol 9.8 per cent. 2) Rate of synthesis of halogenated tyrosines by ${\beta}-tyrosinase$ was slower than that of tyrosine and the rates were decreased in the order of chlorine, bromine and iodine, that is, by increasing the atomic radius. Relative rate of 2-chlorotyrosine synthesis was determined to be 28.2, that of 2-bromotyrosine to be 8.13, and that of 2-iodotyrosine to be 0.98, respectively, against 100 of tyrosine. However 3-iodotyrosine was not synthesized by the enzyme. 3) The relative rate of 2-chlorotyrosine hydrolysis by ${\beta}-tyrosinase$ was 70.7, that of 2-bromotyrosine was 39.0, and that of 2-iodotyrosine was 12.6 against 100 of tyrosine, respectively. The rate of hydrolysis appeared to be decreased in the order of chlorine, bromine and iodine, that is, by increasing the atomic radius or by decreasing the electronegativity. But 3-iodotyrosine was not hydrolyzed by the enzyme. 4) The activity of ${\beta}-tyrosinase$ was inhibited by phenol markedly. Of the halogenated phenols, o-, or m-chlorophenol and o-bromophenol gave marked inhibition on the enzyme action, however inhibition by iodophenol was not strong. Plotting by Lineweaver-Burk method, a mixed-type inhibition by m-chlorophenol was observed and its Ki value was found to be $5.46{\times}10^{-4}M$. 5) During the synthesizing reaction of 2-bromotyrosine by the enzyme, sequential addition of substrate which was m-bromophenol with time intervals and in a small amount resulted in better yield of the product. 6) The halogenated tyrosines which were produced by ${\beta}-tyrosinase$ from pyruvate, ammonia and m-halogenated phenols were analysed to determine their molecular structures by element analysis, NMR spectroscopy, mass spectrometry, and IR spectroscopy. The result indicated that they were 2-chloro-L-tyrosine, 2-bromo-L-tyrosine, and 2-iodo-L-tyrosine, respectively.

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