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INTRINSIC NMR ISOTOPE SHIFTS OF CYCLOOCTANONE AT LOW TEMPERATURE (저온에서의 싸이클로옥타논에 대한 고유동위원소 효과)

  • Jung, Miewon
    • Analytical Science and Technology
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    • v.7 no.2
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    • pp.213-224
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    • 1994
  • Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

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DEGRADATION OF ACID SOLUBLE NUCLEOTIDES AND THEIR RELATED COMPOUNDS IN SEA FOODS DURING PROCESSING AND STORAGE 1. Changes of Nucleotides during Drying Process of the Anchovy, Engraulis japonica (수산식품의 가공 및 보장중의 핵산관련물질의 변화에 관한 연구 1. 마른 멸치 제조과정중의 핵산관련물질의 변화)

  • LEE Eung-Ho;PARK Young-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.4 no.1
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    • pp.31-41
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    • 1971
  • The present study was directed to define the degradation pattern of the nucleotides and their related compounds in the muscle of anchovy during drying. Three kinds of samples, fresh, sun dried and boiled-and-dried anchovy, were prepared and the contents of nucleotides and related compounds of samples were determined by ion exchange chromatography. The results obtained are summarized as follows: Almost all of ATP disappeared in both muscle of sun dried and boiled-and-dried anchovy, although the initial content of ATP in fresh muscle was very low ($1.8{\mu}moles/g$, dry basis). But the remainning amount of ADP was considerably high while the other nucleotide almost entirely disappeared. This suggested that the residual ADP is responsible to the 'bound nucleotide' of myofibrils. In general, AMP content was comparatively lower than that of other nucleotides. Among three samples, the boiled-and-dried sample showed relatively higher AMP value than others. The amount of IMP remained in muscle remarkably varied between the boiled-and-dried anchovy and sun dried anchovy, the former's value being sixteen times higher than that of latter. In the contents of inosine and hypoxanthine, the sun dried anchovy marked an exceedingly high value equivalent to 2.7 times of the boiled-and-dried anchovy. In comparison of the ratio of inosine and hypoxanthine, hypoxanthine was accumulating in boiled-and-dried anchovy whereas inosine was in the sun-dried anchovy. Eighty three percent of total nucleotides in the fresh anchovy retained in the boiled-and-dried anchovy and IMP ratio in total nucleotides was $73\%$. On the contrary, the sun dried anchovy showed barely $10\%$ of retention rate and IMP ratio was only $38\%$. Considered from the flavor quality of dried anchovy, so far as concerned IMP content, it may be said that the boiled-and-drying method is more favorable process for dried product of anchovy than the sun-drying method.

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Effectiveness and characteristics of technology transfer consortia in public R&D sector: The case of Korean TT consortia (공공연구부문에서의 기술이전컨소시엄의 효과와 특성 연구: 공공기술이전컨소시엄 사례를 중심으로)

  • Park, Jong-Bok;Ryu, Tae-Kyu
    • Journal of Korea Technology Innovation Society
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    • v.10 no.2
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    • pp.284-309
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    • 2007
  • Technology transfer (TT) consortium is an affiliation of two or more public research institutions (PRIs) that participate in a common technology transfer activity or pool their resources together, with the objective of facilitating technology transfer. Based on empirical analysis of five regional TT consortia (2002-2006) operating in Korea, this paper suggests their effectiveness by employing a TT performance index (TTPI) and identifies possible characteristics involved, such as motivations, facilitators, barriers, and challenges. TTPI devised in the paper is a new composite TT performance index to measure how much the TT performance of a PH changed in a designated year compared to a base year. All the performance indicators of TTPI are well-structured based on the unique TT process that is prevalent in Korea. Further, TTPI can bring different size and focus of PRIs to the same scale for comparison by double-normalizing. The paper tests the effectiveness of TT consortium for the escalation of TT performances in member PRIs by highlighting the differences of TTPI's between 2005 and 2001. As a result, the paper found that the escalation of TTPI for member PRIs was greater than that for non-member PRIs. As for the characteristics of TT consortia, their respective factors obtained by TT expert survey were computed with proportion tests of differences (Z tests) to compare two perspectives between intramural and extramural groups. One of key findings is that there is general homogeneity in stakeholder perspectives regarding motivations, facilitators, barriers, and challenges. Some notable responses are as follow; the most probable motivation to join TT consortium is to share or exchange TT competences for enhanced performance. Second, the most probable facilitator is professional capability of consortium-hired personnel. Third, the foremost probable barriers to effective TT consortium are frequent change of consortium director and passive participation of member PRIs. Lastly, both publicizing TT consortia and developing performance metrics are the most important for the improvement of TT consortia. The understanding of the characteristics of TT consortia increases the likelihood of accelerated success, because TT consortia path from formation to termination encompasses many concepts, processes, principles, and factors. Finally, an analysis of the survey data combined with expert interview and observation data led the authors to derive five conditions as being critical to viable TT consortia in Korea at early stage of technology transfer systems. These conditions include policy infrastructure, proactive participation, excellent professionals, personal motivation, and teaming mechanisms. It is expected that the Korean evidence is a starting point to develop and refine the theory of TT consortia and for additional studies in other countries.

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Effect of Venture Capitalists on the ChiNext IPO First-Day Return in China (중국 차이넥스트 시장의 벤처캐피탈이 IPO 첫날 수익률에 미치는 영향)

  • Kang, Kai;Ahialey, Joseph Kwaku;Kang, Ho-Jung
    • Management & Information Systems Review
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    • v.36 no.4
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    • pp.117-127
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    • 2017
  • In recent times the size of the world IPO in general has skyrocketed. Specifically, China's financial market development is becoming important as both the size of China's capital market and the number of companies going public are gradually increasing. This has led to a rapid development of venture vapital(VC) institutions in China for the past couple of decades. This study focuses on one of the three markets of China's Shenzhen Stock Exchange-the Growth Enterprise Board((GEB) hereafter, ChiNext). The ChiNext is established in October, 2009 to enable hi-tech or high growth potential technology companies that find it relatively difficult to fulfil the listing requirements of either the Shenzhen Main Board or Small and Medium Size Enterprise Board(SMEB) to go public. This study covers a three-year period(2012/01/-2015/01) and analyze first day initial return of 83 venture capital-backed companies and 53 non-venture capital-backed companies using T-test. Regression analysis is used as to examine the variables affecting IPO's first-day return. The empirical results are four-fold. First, the level of first day return of venture-backed is significantly lower than non venture capital backed support in the Chinese venture capital market. Second, the level of first-day return of listed companies supported by foreign venture capital is significantly higher than that of companies receiving domestic venture capital support. Third, the firms that have a large number of venture capital firms showed a low level of first-day return. Fourth, regression result for the IPO first-day return which is as dependent variable indicates that the venture capital support(VCAP), number of venture capital(VCNum), offering size(Lnsize) and PER all affect have negative effect on the first day initial return. Also, the venture capital type(VCType), turnover ratio and the the firm type(Tech-firms) statistically affect IPO first day return positively. Finally, by shedding more light on the IPO first-day return, this paper provides meaningful information to investors about the Chinese IPO market.

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A Study on the Chemical Index of Alteration of Igneous Rocks (화성암의 화학적 변질지수에 관한 연구)

  • Choi, Eun-Kyeong;Kim, Sung-Wook;Kim, In-Soo;Lee, Kyu-Hwan
    • Journal of the Korean Geotechnical Society
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    • v.28 no.5
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    • pp.41-54
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    • 2012
  • The weathering process of rocks leads to the reduction of geotechnical bearing capacity. The weathering of granite is frequently used to refer to the degradation of geotechnical property in the design and construction of infra-structure. In this study, the range of values of CIA (chemical index of alteration) and the change of mineral compositions by weathering have been analysed with igneous rock, which covers 45.5% in South Korean territory. Several weathering indices were studied for various rocks found in Korea and significant relationships between different indices were delineated via statistical analysis. The applicability of CIA was found to be the most significant among all weathering indicies. The composition of illite, the secondary weathering residual, generally increases for the felsic rock, and swelling clay material is not included. The weathering of felsic rock will follow a sequential process, starting from bed rock, illite, and chlorite to kaoline. The mafic rock will show weathering process, from bed rock, smectite, and chlorite to kaoline. The intermediate rocks such as andesite and tuff will show similar weathering procedure and the composition of kaoline, chlorite, and smectite tends to increase more than that of illite when the mafic rock is dominated. This means the increase of rock material which has high CEC (cation exchange capacity) during secondary weathering process. However, the characteristics of a specific rock cannot be completely analyzed using merely CIA, since it is exclusively based on chemical composition and corresponding alteration. The CIA can be used to quantify the weathering process in a limited range, and further considerations such as rock composition, strength characteristics will be required to configure the comprehensive weathering impact on any specific region.

Effects of Nursery Environmental Factors on the Growth of Pacific Oyste, Crassostrea gigas (양식어장 환경요인이 참굴 (Crassostrea gigas)의 성장에 미치는 영향)

  • 배평암;한창희
    • Journal of Aquaculture
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    • v.11 no.3
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    • pp.391-400
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    • 1998
  • This study was performed to investigate the effects of environmental parameters on the growth of Pacific oyster, Crassostrea gigas at old suspended culturing grounds of Korsung Bay and newly deveoped bottom, culturing grounds of Haenam region located in southern coast of Korea. The Kosung Bay was semiclosed and water exchange occurred through the small mouth and the current speed was very slow as the value of below 0.5kn. Haenam was opened and littoral zone. Current speed of the surroundings of this Bay about to 5.0knand transparency was low with the mean depth of 1.2m by the resuspension of the sediments. Water temperature and salinity regimes were suitable for oysters at those sites, however the mean value of those parameters and seasonal fluctuations was high at Kosung. The mean concentration of dissolved oxygen in survey area was above $5.0mg/\ell$. In Kosung, however, it was decreasing in June and showed the minimum with the concentration of $4.0mg/\ell$ in August at the bottom layer and recovered in September. Eutrophication parameters such as COD were 1.44 mg/l at this location. This mean value was higher than that of the Haenam Bay's $0.96mg/\ell$. The men value of chlorophyll-$\alpha$ at Haenam was two times higher than the other sites. Growth of shell height and meat weight of oysters at Kosung Bay were higher and the fatness was lower compared to thost of Haenam. As a result, absolute growth of oysters was high at Kosung and allometric growth, such as fatness, was good at Haenam. Low water temperature and frequent exposure of oysters to the air during ebb tide may retard the shell growth. On the other hand, relatively high food availability was profitable for the fatness at haenam site.

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Correlation of Tracheal Cross-sectional Area with Parameters of Pulmonary Function in COPD (만성 폐쇄성 폐질환에서 기관의 단면적과 폐기능지표와의 상관관계)

  • Lee, Chan-Ju;Lee, Jae-Ho;Song, Jae-Woo;Yoo, Chul-Gyu;Kim, Young-Whan;Han, Sung-Koo;Shim, Young-Soo;Chung, Hee-Soon
    • Tuberculosis and Respiratory Diseases
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    • v.46 no.5
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    • pp.628-635
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    • 1999
  • Background : Maximal expiratory flow rate is determined by the size of airway, elastic recoil pressure and the collapsibility of airway in the lung. The obstruction of expiratory flow is one of the major functional impairments of emphysema, which represents COPD. Nevertheless, expiratory narrowing of upper airway may be recruited as a mechanism for minimizing airway collapse, and maintaining lung volume and hyperinflation by an endogenous positive end-expiratory pressure in patients with airflow obstruction. We investigated the physiologic role of trachea in respiration in emphysema. Method : We included 20 patients diagnosed as emphysema by radiologic and physiologic criteria from January to August in 1997 at Seoul Municipal Boramae Hospital. Chest roentgenogram, high resolution computed tomography(HRCT), and pulmonary function tests including arterial blood gas analysis and body plethysmography were taken from each patient. Cross-sectional area of trachea was measured according to the respiratory cycle on the level of aortic arch by HRCT and calibrated with body surface area. We compared this corrected area with such parameters of pulmonary function tests as $PaCO_2$, $PaO_2$, airway resistance, lung compliance and so on. Results : Expiratory cross-sectional area of trachea had significant correlation with $PaCO_2$ (r=-0.61, p<0.05), $PaO_2$ (r=0.6, p<0.05), and minute ventilation (r=0.73, p<0.05), but inspiratory cross-sectional area did not (r=-0.22, p>0.05 with $PaCO_2$, r=0.26, p>0.05 with $PaO_2$, and r=0.44, p>0.05 with minute ventilation). Minute ventilation had significant correlation with tidal volume (r=0.45, p<0.05), but it had no significant correlation with respiratory frequency (r=-0.31, p>0.05). Cross-sectional area of trachea had no significant correlation with other parameters of pulmonary function including $FEV_1$, FVC, $FEV_1$/FVC, peak expiratory flow, residual volume, diffusing capacity, airway resistance, and lung compliance, whether the area was expiratory or inspiratory. Conclusion : Cross-sectional area of trachea narrowed during expiration in emphysema, and its expiratory area had significant correlation with $PaCO_2$, $PaO_2$, and minute ventilation.

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Factors Related to the Development of Myocardial Ischemia During Mechanical Ventilation (인공 호흡기 적용에 따른 심근 허혈의 발생에 관한 연구)

  • Kim, Tae-Hyung;Kim, You-Ho;Lim, Chae-Man;Kim, Won;Shim, Tae-Sun;Lee, Sang-Do;Kim, Woo-Sung;Kim, Dong-Soon;Kim, Won-Dong;Koh, Youn-Suck
    • Tuberculosis and Respiratory Diseases
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    • v.46 no.5
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    • pp.645-653
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    • 1999
  • Introduction : Although myocardial ischemia tends to occur more frequently than can he documented in ventilated patients, it has not been well studied on the factors related to the occurrence of the ischemia. Methods : To investigate the related factors to ischemia development, a prospective study was done in 95 cases with consecutive 73 patients who had received mechanical ventilation(MV) in MICU. In addition to 24 h holter monitoring, echocardiogram, electrolytes, cardiac enzymes, hemodynamic, and gas exchange measurements were done within 24 h after initiation of MV in 69 cases. The measurements were repeated at weaning period in 26 cases. The ischemia was defined by the ST segment changes; up-sloping depression more than 1.5 mm or down-sloping or horizontal depression more than 1.0 mm from isoelectric baseline for 80 ms following J point. Results : Twelve patients(12.6% in 95 cases) developed ischemia in total. The incidence of ischemia development showed an increased tendency in the initial 24 hr after MV (15.9%) and in patients with left-sided heart failure found by echocardiogram (18.2%) compared with that of the weaning period (3.8%) and patients without heart failure (10.9%) (P=0.12, P=0.09, in each). There were no differences in APACHE III score, baseline ECG findings, electrolytes abnormalities, use of inotropics or bronchodilators, presence of sepsis or shock, mode of ventilation, and survival rate according to the development of ischemia. Maximal heart rates and mean arterial pressure also were not different between patients with ($137.2{\pm}30.9/min$, $82.5{\pm}15.9$ mm Hg) and without ischemia ($l29.5{\pm}29.7/min$, $83.8{\pm}17.6$ mm Hg). Conclusion : Although the incidence of myocardial ischemia was 12.6% in total, there were no clinically predictable factors to the development of ischemia during mechanical ventilation.

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Amendments and Construction Systems for Improving the Performance of Sand-Based Putting Greens (골프장 putitng green 개선을 위한 토양 개량제와 green 구조시설)

  • Ok Chang-Ho;Anderson Stephen H.;Ervin Erik H.
    • Asian Journal of Turfgrass Science
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    • v.18 no.3
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    • pp.149-163
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    • 2004
  • Physical and chemical properties of root zone mixes and methods of green construction are important considerations for improving turf grass quality for putting greens. This study compared Penncross creeping bentgrass (Agrostis palustris Huds.) performance as affected by three root zone construction systems with three amendments (sand, peat, and zeolite). The objective of this study was to determine if an amended California construction system would improve green performance during establishment (1998-1999) and maturation (2000-2001). Three treatments were tested: California ($100\%$ sand), USGA($90\%$ sand and $10\%$ peat, v/v), and California-Z ($85\%$ sand and $15\%$ zeolite, v/v). Treatments were arranged in a randomized complete block with four replicates. Physical and chemical properties of the root zone and bentgrass performance were compared for the treatments. The California-Z treatment had the highest saturated hydraulic conductivity, field infiltration rate and the lowest bulk density. It also had the highest cation exchange capacity and plant available nutrient concentrations among the three treatments. The California-Z treatment produced bentgrass quality and color during green establishment and maturation that were equal to or higher than the California treatment, and consistently higher than the USGA treatment. The addition of an inorganic amendment to the California system improved physical and chemical properties of the root zone and improved quality and color of bentgrass during green establishment. During green maturation, creeping bentgrass in the California-Z treatment was equal (6 of 15 sampling dates) or $20\%$ higher (9 of 15 dates) in quality compared to the California system.

The study on payment system improvement in Korean firms : The impacts of stock options on pay equity, job attitude and intention to turnover (한국 기업의 보상제도 개선을 통한 경쟁력 제고 방안 : 스톡옵션의 부여에 관한 인식과 보상공정성, 직무태도 및 이직의도와의 관계에 관한 연구)

  • Cha, Sung-Ho;Yang, Dong-Hoon
    • Journal of the Korea Society of Computer and Information
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    • v.16 no.2
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    • pp.267-278
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    • 2011
  • This study examines the relationship among stock options, pay equity, organizational commitment. Employees who received stock options tend to perceive their pay more equitable and the tendency shows a positive relationship among the amount of stock options and the equity perception. Also employees who received stock options perceive greater procedural equity, as they recognize stock options are awarded to many employees. However, the perception of stock options was not significantly associated with organizational commitment, turnover intention, and pay satisfaction. In 2003, the study surveyed 115 employees who received stock options in 10 publicly owned Korean firms that introduced stock option plans. The statistical analysis leads to the conclusions as follows. First, as the number of stock options increases, the receiver tends to perceive that pay system is more distributively equitable. Second, as the number of stock option receivers increases, the employees perceive the pay system more procedurally equitable. Third, stock option payments don't ensure that it improves pay satisfaction, turnover intention, and organizational commitment. This study shows a positive relationship that stock options work favorably in terms of pay equity, but the effect doesn't seem to be widely positive. The reason is that the introduction of stock options in domestic firms has been made only recently after the foreign exchange crisis in the late 1990s. More experiments and design issues should be discussed for the future.