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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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Availability of Heavy Metals in Soils with Different Characteristics and Controversial Points for Analytical Methods of Soil Contamination in Korea (토양특성별 중금속 유효도와 토양오염 평가방법의 개선점)

  • Jung, Goo-Bok;Kim, Won-Il;Lee, Jong-Sik;Shin, Joung-Du;Kim, Jin-Ho;Yun, Sun-Gang
    • Korean Journal of Environmental Agriculture
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    • v.24 no.2
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    • pp.106-116
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    • 2005
  • This experiment was conducted to investigate available extraction capacity and potential mobility of heavy metal according to the distribution property and contamination level of heavy metals in soils and to suggest a reform measure of soil environment assessment methodology applied with soil quality and the official soil heavy metal test methods in domestic and foreign countries. The soils were collected from the natural forest paddy with long-term application of same type fertilizer, and paddies near metal mine and industrial complex. The post-treatment methods of soil were partial extraction, acid digestion and sequential extraction methods. For the heavy metal contents with different soil properties, it was shown that their natural forest and paddy soil were slightly low and similar to the general paddy soil, while their paddies near metal mine and industrial complex were higher than the standard level of Soil Environment Protection Act. Heavy metal concentrations in the soils with different soil properties had difference between $HNO_3\;and\;HNO_3+HCl$ extractant by US-EPA 3051a method. There were highly significant positive relationships in both two methods. It was appeared that the higher extractable concentration ratio with 0.1N-HCl to total heavy metal content with $HNO_3+HCl$ extractant the greater total heavy metal content. There were highly significant positive correlationship between total heavy metal content and extractable content with 0.1N-HCl. For extractable capacity of soil extractable solution compared to the total heavy metal content it was appeared that it extractable method with 0.1N-HCl was higher than those with EDTA and DTPA. In extractable ratio with 0.1N-HCl in the contaminated paddy soils near mine and industrial complex, it was shown that the lower soil pH, the higher total heavy metal content. The order of a potential mobility coefficient by distribution of heavy metal content with ie different typies in the soil was Cd>Ni>Zn>Cu>Pb. It could be known that contamination characteristics of heavy metals with different types of soils were affected by different heavy metal components, contamination degree and soil chemical properties, and heavy metal concentration with different extractable methods had great variations with adjacent environment. To be compared with assessment methodology of soil environment impact at domestic and foreign countries with our results, it might be considered that there was necessary to make a single analysis method based on total heavy metal content with environmental overloading concept because of various analysis methods for total heavy metal content and present analysis method with great variation according to soil environment. In spite of showing higher concentration of heavy metal with acidic digestion than the extractable method, it might be considered that there is need to be adjusted the national standard of soil heavy metal contamination.

A Study on the Marketplace Models for Korean Animation Content Foreign Sales (국산 애니메이션 콘텐츠 해외 판매를 위한 마켓플레이스 모델 연구)

  • Han, Sang-Gyun
    • Cartoon and Animation Studies
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    • s.44
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    • pp.333-361
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    • 2016
  • In general, content business companies include animation industry can have benefits, which they have higher incomes when they obtain wider markets. Therefore, they pursue to have diverse windows for content distribution or to reach the foreign markets for dealing their content products with potential customers. It have the greatest value. They can re-invest the incomes to produce their new products, and they can enhance the international competitiveness of their next products. As the results, the companies can have more incomes and wider markets in next business, and it will be the effectiveness of the good cycle of the animation industry. Animation industry has being undergone of its structure changes, more economical chances and viewers' attitudes changes through the all over the industry because of the acceptance of new digital technology. To response the changes or have the new chances from the changes, they should to review the existing system and the law concerned with the animation business as well as having the diverse new plans for supporting the industry like a construction of the online marketplace of Korean animation. It would make the Korean animation companies to meet foreign customers easily by making lower the entrance barrier of the foreign markets. Current Korean government needs to estimate the value of the Korean animation accurately and objectively by concerning its surroundings to support efficiently. However, it is very difficult to estimate the value of the content rightly because of its' intangible and subjective matter. For this, they should analyze the all the data of the information of the Korean animation content by accumulate, open to the public and manage. So if the government makes online marketplace for the Korean animation, which all the Korean animation companies get in, it would be a solution of estimating the value of the Korean animation rightly. In addition, it will be used as the role of archive of the government to lead the industry successfully. As a point of the small size of the Korean animation companies, they are government dependable because of its low budget, so they strongly expect the government to do the right role as the unique knowledge distributor. Therefore, the Korean animation online marketplace would make not only big companies, but also small companies to have the chances to increase the value of their content in the global markets by themselves without economic burdens.

Cellular Protective Effect and Liposome Formulation for Enhanced Transdermal Delivery of Persicaria hydropiper L. Extract (여뀌 추출물의 세포 보호 작용과 피부 흡수 증진을 위한 리포좀 제형 연구)

  • Kim, Jung-Eun;Lee, Hye-Jin;Lim, Myoung-Sun;Park, Min-A;Park, Soo-Nam
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.38 no.1
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    • pp.15-31
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    • 2012
  • In our previous studies, the antioxidant, anti-aging, and antibacterial activities of Persicaria hydropipier L. extract, and the moisturizing effect of cream containing P. hydropipier extract were investigated. In this study, the cellular protective effects of P. hydropipier extract and isoquercitrin, main component from P. hydropipier in $^1O_2$-induced photohemolysis of human erythrocytes and ultraviolet B (UVB)-exposed HaCaT cells were investigated. Liposomes such as ethosome and elastic liposome for enhanced transdermal delivery were prepared. Size, loading efficiency, stability, and cumulative permeated amounts of ethosomes and elastic liposomes were evaluated. P. hydropipier extract and isoquercitrin showed more prominent cellular protective effect than (+)-${\alpha}$-tocopherol, known as lipid antioxidant at $5{\mu}g/mL$. P. hydropipier extract didn't show any characteristics of cytotoxicity at $50{\mu}g/mL$. When HaCaT cells were exposed to a single large dose ($400mJ/cm^2$) of UVB, the extract protected the cells against UVB radiation in a concentration dependent manner ($12.5{\sim}50{\mu}g/mL$). Cell viability of HaCaT cells exposed to UVB $400mJ/cm^2$ was increased by treatment with P. hydropipier extract or isoquercitrin from 36 % (cell viability of positve control groups) to 90 % (cell viability of P. hydropipier extract or isoquercitrin- treated groups). The size of 0.04 % P. hydropiper extract loaded ethosomes was 173.0 nm and the loading efficiency was 55.58 %. 0.04 % P. hydropiper extract loaded ethosomes were stable with as monodisperse particles for 1 week. The ethosome exhibited more skin permeability than general liposome and ethanol solution. The optimal ratio of lipid to surfactant ($Tego^{(R)}$ care 450) of 0.1 % P. hydropiper extract loaded elastic liposomes was observed to be 95 : 5. Vesicle size of 0.1 % P. hydropiper extract loaded elastic liposome was 176.5 nm. The deformability index of the elastic liposome was 16.4. The loading efficiency was 68.8 %. The elastic liposome containing P. hydropiper extract showed more skin permeability than liposome without surfactant ($Tego^{(R)}$ care 450).

Chemical Reactions in Surfactant Solutions (Ⅳ) : Micellar Rate Effect on Reactions of Hydroxide and o-Iodosobenzoate Ions with Organic Phosphinates (계면활성제 용액속에서의 화학반응 (제 4 보) : $OH^-$ 및 o-Iodosobenzoate 이온에 의한 유기 포스피네이트의 탈인산화 반응에 미치는 CTAX 미셀의 영향)

  • Hong, Yeong Seok;Kim, Hyeon Muk
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.753-762
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    • 1994
  • Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

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The characteristic of InGaN/GaN MQW LED by different diameter in selective area growth method (선택성장영역 크기에 따른 InGaN/GaN 다중양자우물 청색 MOCVD-발광다이오드 소자의 특성)

  • Bae, Seon-Min;Jeon, Hun-Soo;Lee, Gang-Seok;Jung, Se-Gyo;Yoon, Wi-Il;Kim, Kyoung-Hwa;Yang, Min;Yi, Sam-Nyung;Ahn, Hyung-Soo;Kim, Suck-Whan;Yu, Young-Moon;Ha, Hong-Ju
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.22 no.1
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    • pp.5-10
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    • 2012
  • In general, the fabrications of the LEDs with mesa structure are performed grown by MOCVD method. In order to etch and separate each chips, the LEDs are passed the RIE and scribing processes. The RIE process using plasma dry etching occur some problems such as defects, dislocations and the formation of dangling bond in surface result in decline of device characteristic. The SAG method has attracted considerable interest for the growth of high quality GaN epi layer on the sapphire substrate. In this paper, the SAG method was introduced for simplification and fabrication of the high quality epi layer. And we report that the size of selective area do not affect the characteristics of original LED. The diameter of SAG circle patterns were choose as 2500, 1000, 350, and 200 ${\mu}m$. The SAG-LEDs were measured to obtain the device characteristics using by SEM, EL and I-V. The main emission peaks of 2500, 1000, 350, and 200 ${\mu}m$ were 485, 480, 450, and 445 nm respectively. The chips of 350, 200 ${\mu}m$ diameter were observed non-uniform surface and resistance was higher than original LED, however, the chips of 2500, 1000 ${\mu}m$ diameter had uniform surface and current-voltage characteristics were better than small sizes. Therefore, we suggest that the suitable diameter which do not affect the characteristic of original LED is more than 1000 ${\mu}m$.

Spatial problems of Korea -A delphi survey- (國土管理의 方向定立을 위한 國土診斷 -專門家 集團의 問題意識을 中心으로-)

  • Kim, Inn;Yu, Woo-Ik;Huh, Woo-Kung;Park, Young-Han;Park, Sam-Ock;Yu, Keun-bae;Choi, Byung-Seon
    • Journal of the Korean Geographical Society
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    • v.29 no.1
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    • pp.16-38
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    • 1994
  • The spatial structure of Korea has been changed drastically during the second half of this century. The events such as the Korean War and the resultant division of the Korean Peninsular into two Koreas, rapid industrialization and urbanization are the major causes among others for the spatial changes of the nation. The changes in turn have spawned a number of spatial problems. It is time, we argue, to diagnose how much the nation is now ill-structured, and to discuss of which directions the long-term spatial management be reoriented. A delphi survey was conducted during the early 1993 to fulfill such research needs. Questionnaires were distributed among geographers, planners, and high governmental officials throughout the nation. These 'experts of spatial problems' were requested to evaluate the past spatial policies and strategies, and to identify spatial and environmental problems at the national, regional and local levels. The survey included questions with regard to the spatial problems in North Korea too. A complementary literature survey in the fields of spatial sciences was accomplished as well in order to identify the major research interests and issues with regard to the nations's spatial structure. The delphi survey results indicatee that the present spatial structure: in relation to consumption, housing and economic activities is satisfactory in overall, while rather poor in terms of education, leisure and community activities. Most of the experts consider infrastructural improvements are urgent in the areas of roads, waste disposal facilitles, railroads, harbors, water supply and drainage systems. The over-concentration of economic, social and political function in the Seoul Metropolitan Region is perceived to be the most serious spatial problem in Korea. The long-term solutions suggested are strategies toward a more balanced regional development as well as toward a cleaner environment. The concensus among the experts for the short-term solution is the redistribution of population and industries from the Seoul Metropolitan Region to the intermediate and small cities. The land use policies and concurrent large-scale infrastructural projects are evaluated largely pertinent and desirable in general. It is, however, suggested that development projects be conducted in a more harmonious way with environment. The survey respondents suggest that the present environmental management policies should be reexamined critically. With regard to regional and local problems, transportation and pollutions are thought to be most serious in the Seoul Metropolitan Region, while employment opportunities, and information, education and health care services are most deprived in small cities and rural areas. The majority of the experts consider a city size of 250, 000-500, 000 population is desirable to live within. Respondents beileve that North Korea's physical environment is still not aggravated much whereas its infrastructural provisions are largely pool. The co-authors of this research figure a "environmentaly sound and spatially balanced Korean Penninsular" as the ideal type of spatial structure in Korea. The basic guidelines toward this ideal prototype are suggested: the recovery of spetial integrity, progressive restructuring of the nation, land uses geared to public welfare rather than private interests, and eco-humanistic approach in spatial policies.

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Effects of Surface Finishes on the Low Cycle Fatigue Characteristics of Sn-based Pb-free Solder Joints (금속패드가 Sn계 무연솔더의 저주기 피로저항성에 미치는 영향)

  • Lee, Kyu-O;Yoo, Jin
    • Journal of the Microelectronics and Packaging Society
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    • v.10 no.3
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    • pp.19-27
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    • 2003
  • Surface finishes of PCB laminates are important in the solder joint reliability of flip chip package because the types and thicknesses of intermetallic compound(IMC), and compositions and hardness of solders are affected by them. In this study, effects of surface finishes of PCB on the low cycle fatigue resistance of Sn-based lead-free solders; Sn-3.5Ag, Sn-3.5Ag-XCu(X=0.75, 1.5), Sn-3.5Ag-XBi(X=2.5, 7.5) and Sn-0.7Cu were investigated for the Cu and Au/Ni surface finish treatments. Displacement controlled room temperature lap shear fatigue tests showed that fatigue resistance of Sn-3.5Ag-XCu(X=0.75, 1.5), Sn-3.5Ag and Sn-0.7Cu alloys were more or less the same each other but much better than that of Bi containing alloys regardless of the surface finish layer used. In general, solder joints on the Au/Ni finish showed better fatigue resistance than those on the Cu finish. Cross-sectional fractography revealed microcracks nucleation inside of the interfacial IMC near the solder mask edge, more frequently on the Cu than the Au/Ni surface finish. Macro cracks followed the solder/IMC interface in the Bi containing alloys, while they propagated in the solder matrix in other alloys. It was ascribed to the Bi segregation at the solder/IMC interface and the solid solution hardening effect of Bi in the $\beta-Sn$ matrix.

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Radiology Department Infection Control According to Radiography Frequency and Disinfection Period (촬영 빈도수 및 소독 주기에 따른 영상의학과 감염 관리)

  • Lee, Jae-Seung;Jeong, Kyu-Hwan;Kim, Gyoung-Hee;Im, In-Chul;Kweon, Dae-Cheol;Goo, Eun-Hoe;Dong, Kyung-Rae;Chung, Woon-Kwan
    • Journal of the Korean Society of Radiology
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    • v.5 no.2
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    • pp.73-80
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    • 2011
  • Questionnaires were distributed to Radiology departments at hospitals with 300 sickbeds throughout the Pohang region of North Gyeongsang Province concerning awareness and performance levels of infection control. The investigation included measurements of the pollution levels of imaging equipment and assistive apparatuses in order to prepare a plan for the activation of prevention and management of hospital infections. The survey was designed to question respondents in regards to personal data, infection management prevention education, and infection management guidelines. The ATP Public Heath Monitering System was used to measure seven items for pollution levels of imaging equipment and assistive apparatuses in the Radiology Department. Data was analysed using SPSS version 12.0 for paired t-test and Pearson coefficient with a statistically significant level of 0.05. The results of the survey showed a total awareness level of infection management prevention education averaged at $3.73{\pm}0.64$ and performance levels resulted at $3.39{\pm}0.83$ which were statistically significant (p = 0.01). Also the measurements of pollution levels for equipment with high patient contact showed a Pearson Coefficient of over 0.5 implying a focus on pathogenic bacterium. There was no statistical significance with the frequency of imaging (p < 0.05). Therefore for general hospitals with high patient contact, there is a need to supply analyzing equipment for real time monitoring and the implementation of disinfection management that uses a Ministry of Health and Welfare approved antiseptic solution twice every minute.

Diagnostic Classification of Chest X-ray Pneumonia using Inception V3 Modeling (Inception V3를 이용한 흉부촬영 X선 영상의 폐렴 진단 분류)

  • Kim, Ji-Yul;Ye, Soo-Young
    • Journal of the Korean Society of Radiology
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    • v.14 no.6
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    • pp.773-780
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    • 2020
  • With the development of the 4th industrial, research is being conducted to prevent diseases and reduce damage in various fields of science and technology such as medicine, health, and bio. As a result, artificial intelligence technology has been introduced and researched for image analysis of radiological examinations. In this paper, we will directly apply a deep learning model for classification and detection of pneumonia using chest X-ray images, and evaluate whether the deep learning model of the Inception series is a useful model for detecting pneumonia. As the experimental material, a chest X-ray image data set provided and shared free of charge by Kaggle was used, and out of the total 3,470 chest X-ray image data, it was classified into 1,870 training data sets, 1,100 validation data sets, and 500 test data sets. I did. As a result of the experiment, the result of metric evaluation of the Inception V3 deep learning model was 94.80% for accuracy, 97.24% for precision, 94.00% for recall, and 95.59 for F1 score. In addition, the accuracy of the final epoch for Inception V3 deep learning modeling was 94.91% for learning modeling and 89.68% for verification modeling for pneumonia detection and classification of chest X-ray images. For the evaluation of the loss function value, the learning modeling was 1.127% and the validation modeling was 4.603%. As a result, it was evaluated that the Inception V3 deep learning model is a very excellent deep learning model in extracting and classifying features of chest image data, and its learning state is also very good. As a result of matrix accuracy evaluation for test modeling, the accuracy of 96% for normal chest X-ray image data and 97% for pneumonia chest X-ray image data was proven. The deep learning model of the Inception series is considered to be a useful deep learning model for classification of chest diseases, and it is expected that it can also play an auxiliary role of human resources, so it is considered that it will be a solution to the problem of insufficient medical personnel. In the future, this study is expected to be presented as basic data for similar studies in the case of similar studies on the diagnosis of pneumonia using deep learning.