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Development and Validation of the Analytical Method for Oxytetracycline in Agricultural Products using QuEChERS and LC-MS/MS (QuEChERS법 및 LC-MS/MS를 이용한 농산물 중 Oxytetracycline의 잔류시험법 개발 및 검증)

  • Cho, Sung Min;Do, Jung-Ah;Lee, Han Sol;Park, Ji-Su;Shin, Hye-Sun;Jang, Dong Eun;Cho, Myong-Shik;Jung, ong-hyun;Lee, Kangbong
    • Journal of Food Hygiene and Safety
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    • v.34 no.3
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    • pp.227-234
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    • 2019
  • An analytical method was developed for the determination of oxytetracycline in agricultural products using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method by liquid chromatography-tandem mass spectrometry (LC-MS/MS). After the samples were extracted with methanol, the extracts were adjusted to pH 4 by formic acid and sodium chloride was added to remove water. Dispersive solid phase extraction (d-SPE) cleanup was carried out using $MgSO_4$ (anhydrous magnesium sulfate), PSA (primary secondary amine), $C_{18}$ (octadecyl) and GCB (graphitized carbon black). The analytes were quantified and confirmed with LC-MS/MS using ESI (electrospray ionization) in positive ion MRM (multiple reaction monitoring) mode. The matrix-matched calibration curves were constructed using six levels ($0.001{\sim}0.25{\mu}g/mL$) and coefficient of determination ($r^2$) was above 0.99. Recovery results at three concentrations (LOQ, $10{\times}LOQ$, and $50{\times}LOQ$, n=5) were from 80.0 to 108.2% with relative standard deviations (RSDs) less than of 11.4%. For inter-laboratory validation, the average recovery was in the range of 83.5~103.2% and the coefficient of variation (CV) was below 14.1%. All results satisfied the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the Food Safety Evaluation Department guidelines (2016). The proposed analytical method was accurate, effective and sensitive for oxytetracycline determination in agricultural commodities. This study could be useful for safety management of oxytetracycline residues in agricultural products.

Improvement and Validation of an Analytical Method for Quercetin-3-𝑜-gentiobioside and Isoquercitrin in Abelmoschus esculentus L. Moench (오크라 분말의 Quercetin-3-𝑜-Gentiobioside 및 Isoquercitrin의 분석법 개선 및 검증)

  • Han, Xionggao;Choi, Sun-Il;Men, Xiao;Lee, Se-jeong;Jin, Heegu;Oh, Hyun-Ji;Cho, Sehaeng;Lee, Boo-Yong;Lee, Ok-Hwan
    • Journal of Food Hygiene and Safety
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    • v.37 no.2
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    • pp.39-45
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    • 2022
  • This study aimed to investigate the validation and modify the analytical method to determine quercetin-3-𝑜-gentiobioside and isoquercitrin in Abelmoschus esculentus L. Moench for the standardization of ingredients in development of functional health products. The analytical method was validated based on the ICH (International Conference for Harmonization) guidelines to verify the reliability and validity there of on the specificity, linearity, accuracy, precision, detection limit and quantification limit. For the HPLC analysis method, the peak retention time of the index component of the standard solution and the peak retention time of the index component of A. esculentus L. Moench powder sample were consistent with the spectra thereof, confirming the specificity. The calibration curves of quercetin-3-𝑜-gentiobioside and isoquercitrin showed a linearity with a near-one correlation coefficient (0.9999 and 0.9999), indicating the high suitability thereof for the analysis. A. esculentus L. Moench powder sample of a known concentration were prepared with low, medium, and high concentrations of standard substances and were calculated for the precision and accuracy. The precision of quercetin-3-𝑜-gentiobioside and isoquercitrin was confirmed for intra-day and daily. As a result, the intra-day precision was found to be 0.50-1.48% and 0.77-2.87%, and the daily precision to be 0.07-3.37% and 0.58-1.37%, implying an excellent precision at level below 5%. As a result of accuracy measurement, the intra-day accuracy of quercetin-3-𝑜-gentiobioside and isoquercitrin was found to be 104.87-109.64% and the daily accuracy thereof was found to be 106.85-109.06%, reflecting high level of accuracy. The detection limits of quercetin-3-𝑜-gentiobioside and isoquercitrin were 0.24 ㎍/mL and 0.16 ㎍/mL, respectively, whereas the quantitation limits were 0.71 ㎍/mL and 0.49 ㎍/mL, confirming that detection was valid at the low concentrations as well. From the analysis, the established analytical method was proven to be excellent with high level of results from the verification on the specificity, linearity, precision, accuracy, detection limit and quantitation limit thereof. In addition, as a result of analyzing the content of A. esculentus L. Moench powder samples using a validated analytical method, quercetin-3-𝑜-gentiobioside was analyzed to contain 1.49±0.01 mg/dry weight g, while isoquercitrin contained 1.39±0.01 mg/dry weight g. The study was conducted to verify that the simultaneous analysis on quercetin-3-𝑜-gentiobioside and isoquercitrin, the indicators of A. esculentus L. Moench, is a scientifically reliable and suitable analytical method.

Studies on Press Drying of Fire-Retardant Treated Plywood (내화처리합판(耐火處理合板)의 열판건조(熱板乾燥)에 관(關)한 연구(硏究))

  • Kim, Jong Man
    • Journal of Korean Society of Forest Science
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    • v.56 no.1
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    • pp.1-25
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    • 1982
  • Plywood used for construction as a decorative inner material is inflammable and can cause fire accidents. causing destruction of human life and property. To diminish the fire disaster, fire retardant plywood is indeed required. In the methods of manufacturing the fire retardant plywood, a soaking method is occasionally used. However after soaking plywood into fire retardant chemical solutions redrying of soaked plywood is of the utmost importance. In this study 3.5mm and 5.0mm thickness plywoods were selected for fire retardant treatment. Treating solutions were prepared for 20% dilute solutions of ammonium sulfate, monoammonium phosphate, diammonium phosphate, borax-boric acid minalith, and water solution, 1-, 3-, 6-, and 9 hour-soaking treatments in borax-boric acid and minalith, and 6- and 9 hours in the other chemicals were applied and after the treatment hot drying was applied to treated plywoods at $90^{\circ}C$, $120^{\circ}C$ and $150^{\circ}C$ of press temperature. Drying rates, drying curves, water absorption rates of fire retardant chemicals, weight per volume and fire retardant degree of plywood were investigated. The results may be summarized as follows: 1) In the 9 hours-soaking treatment of fire retardants by hot and cold bath method, the chemical retentions of 3.5mm thickness plywood could be attained within the range ($1.125-2.25kg/(30cm)^3$) of minimum retention specification as follows: $1.353kg/(30cm)^3$ in monoammonium phosphate, $1.331kg/(30cm)^3$ in diammonium phosphate, $1.263kg/(30cm)^3$ in ammonium sulfate, $1.226kg/(30cm)^3$ in borax-boric acid. But the chemical retention, $0.906kg/(30cm)^3$, in minalith could not be attained within the range of minimum retention specification. And also in case of 5.0mm thickness plywood, chemical retentions, as $1.356kg/(30cm)^3$ and $1.166kg/(30cm)^3$ respectively, of ammonium sulfate and diammonium phosphate could be attained within the range minimum retention specification, but the other fire retardant chemicals could not. 2) In the 6- and - hours-soaking treatments of 3.5mm and 5.0mm thickness plywood, the drying curve sloped of chemical treated plywood was smaller than that of water treated. The drying rate related to thickness of treated plywood, was about three times as fast in 3.5mm thickness plywood compared with 5.0mm thickness plywood. 3) In the treatment at $120^{\circ}C$ of hot platen temperature, the drying rates of chemical-treated plywood showed the highest quantity in diammonium phosphate of 3.5mm and 5.0mm thickness plywood. But the drying rate of water treated plywood was highest during the 6- and 9 hours-soaking treatments. 4) The drying rate remarkably increased with proportion to increase of the platen temperature, and the values were respectively 1.23%/min., 6.54%/min., 25.75%/min. in hot platen temperature of $90^{\circ}C$, $120^{\circ}C$, $150^{\circ}C$ in 3.5mm thickness plywood and 0.55%.min., 2.49%/min., 8.19%/min. in hot platen temperature of $90^{\circ}C$, $120^{\circ}C$, $150^{\circ}C$ in 5.0mm thickness plywood. 5) In the fire retardant degree of chemical treated plywood, the loss in weight was the smallest in diammonium phosphate, next was in monoammonium phosphate and ammonium sulfate, and the greatest was in borax-boric acid and minalith. And the fire-retardant effect in burning time, flame-exhausted time and carbonized area were greatest in diammouniun phosphate, next were in monoammonium phosphate and ammonium sulfate, and the weakest were in borax-boric acid and minalith.

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Studies on the Physical and Chemical Denatures of Cocoon Bave Sericin throughout Silk Filature Processes (제사과정 전후에서의 견사세리신의 물리화학적 성질변화에 관한 연구)

  • 남중희
    • Journal of Sericultural and Entomological Science
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    • v.16 no.1
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    • pp.21-48
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    • 1974
  • The studies were carried out to disclose the physical and chemical properties of sericin fraction obtained from silk cocoon shells and its characteristics of swelling and solubility. The following results were obtained. 1. The physical and chemical properties of sericin fraction. 1) In contrast to the easy water soluble sericin, the hard soluble sericin contains fewer amino acids include of polar side radical while the hard soluble amino acid sach as alanine and leucine were detected. 2) The easy soluble amino acids were found mainly on the outer part of the fibroin, but the hard soluble amino acids were located in the near parts to the fibroin. 3) The swelling and solubility of the sericin could be hardly assayed by the analysis of the amino acid composition, and could be considered to tee closely related to the compound of the sericin crystal and secondary structure. 4) The X-ray patterns of the cocoon filament were ring shape, but they disappeared by the degumming treatment. 5) The sericin of tussah silkworm (A. pernyi), showed stronger circular patterns in the meridian than the regular silkworm (Bombyx mori). 6) There was no pattern difference between Fraction A and B. 7) X-ray diffraction patterns of the Sericin 1, ll and 111 were similar except interference of 8.85A (side chain spacing). 8) The amino acids above 150 in molecular weight such as Cys. Tyr. Phe. His. and Arg. were not found quantitatively by the 60 minutes-hydrolysis (6N-HCI). 9) The X-ray Pattern of 4.6A had a tendency to disappear with hot-water, ether, and alcohol treatment. 10) The partial hydrolysis of sericin showed a cirucular interference (2A) on the meridian. 11) The sericin pellet after hydrolysis was considered to be peptides composed with specific amino acids. 12) The decomposing temperature of Sericin 111 was higher than that of Sericin I and II. 13) Thermogram of the inner portioned sericin of the cocoon shell had double endothermic peaks at 165$^{\circ}C$, and 245$^{\circ}C$, and its decomposing temperature was higher than that of other portioned sericin. 14) The infrared spectroscopic properties among sericin I, II, III and sericin extracted from each layer portion of the cocoon shell were similar. II. The characteristics of seriein swelling and solubility related with silk processing. 1) Fifteen minutes was required to dehydrate the free moisture of cocoon shells with centrifugal force controlled at 13${\times}$10$^4$ dyne/g at 3,000 R.P.M. B) It took 30 minutes for the sericin to show positive reaction with the Folin-Ciocaltue reagent at room temperature. 3) The measurable wave length of the visible radiation was 500-750m${\mu}$, and the highest absorbance was observed at the wave length of 650m${\mu}$. 4) The colorimetric analysis should be conducted at 650mu for low concentration (10$\mu\textrm{g}$/$m\ell$), and at 500m${\mu}$ for the higher concentration to obtain an exact analysis. 5) The absorbing curves of sericin and egg albumin at different wave lengths were similar, but the absorbance of the former was slightly higher than that of the latter. 6) The quantity of the sericin measured by the colorimetric analysis, turned out to be less than by the Kjeldahl method. 7) Both temperature and duration in the cocoon cooking process has much effect on the swelling and solubility of the cocoon shells, but the temperature was more influential than the duration of the treatment. 8) The factorial relation between the temperature and the duration of treatment of the cocoon cooking to check for siricin swelling and solubility showed that the treatment duration should be gradually increased to reach optimum swelling and solubility of sericin with low temperature(70$^{\circ}C$) . High temperature, however, showed more sharp increase. 9) The more increased temperature in the drying of fresh cocoons, the less the sericin swelling and solubility were obtained. 10) In a specific cooking duration, the heavier the cocoon shell is, the less the swelling and solubility were obtained. 11) It was considered that there are differences in swelling or solubility between the filaments of each cocoon layer. 12) Sericin swelling or solubility in the cocoon filament was decreased by the wax extraction.. 13) The ionic surface active agent accelerated the swelling and solubility of the sericin at the range of pH 6-7. 14) In the same conditions as above, the cation agent was absorbed into the sericin. 15) In case of the increase of Ca ang Mg in the reeling water, its pH value drifted toward the acidity. 16) A buffering action was observed between the sericin and the water hardness constituents in the reeling water. 17) The effect of calcium on the swelling and solubility of the sericin was more moderate than that of magnecium. 18) The solute of the water hardness constituents increased the electric conductivity in the reeling water.

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An accuracy analysis of Cyberknife tumor tracking radiotherapy according to unpredictable change of respiration (예측 불가능한 호흡 변화에 따른 사이버나이프 종양 추적 방사선 치료의 정확도 분석)

  • Seo, jung min;Lee, chang yeol;Huh, hyun do;Kim, wan sun
    • The Journal of Korean Society for Radiation Therapy
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    • v.27 no.2
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    • pp.157-166
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    • 2015
  • Purpose : Cyber-Knife tumor tracking system, based on the correlation relationship between the position of a tumor which moves in response to the real time respiratory cycle signal and respiration was obtained by the LED marker attached to the outside of the patient, the location of the tumor to predict in advance, the movement of the tumor in synchronization with the therapeutic device to track real-time tumor, is a system for treating. The purpose of this study, in the cyber knife tumor tracking radiation therapy, trying to evaluate the accuracy of tumor tracking radiation therapy system due to the change in the form of unpredictable sudden breathing due to cough and sleep. Materials and Methods : Breathing Log files that were used in the study, based on the Respiratory gating radiotherapy and Cyber-knife tracking radiosurgery breathing Log files of patients who received herein, measured using the Log files in the form of a Sinusoidal pattern and Sudden change pattern. it has been reconstituted as possible. Enter the reconstructed respiratory Log file cyber knife dynamic chest Phantom, so that it is possible to implement a motion due to respiration, add manufacturing the driving apparatus of the existing dynamic chest Phantom, Phantom the form of respiration we have developed a program that can be applied to. Movement of the phantom inside the target (Ball cube target) was driven by the displacement of three sizes of according to the size of the respiratory vertical (Superior-Inferior) direction to the 5 mm, 10 mm, 20 mm. Insert crosses two EBT3 films in phantom inside the target in response to changes in the target movement, the End-to-End (E2E) test provided in Cyber-Knife manufacturer depending on the form of the breathing five times each. It was determined by carrying. Accuracy of tumor tracking system is indicated by the target error by analyzing the inserted film, additional E2E test is analyzed by measuring the correlation error while being advanced. Results : If the target error is a sine curve breathing form, the size of the target of the movement is in response to the 5 mm, 10 mm, 20 mm, respectively, of the average $1.14{\pm}0.13mm$, $1.05{\pm}0.20mm$, with $2.37{\pm}0.17mm$, suddenly for it is variations in breathing, respective average $1.87{\pm}0.19mm$, $2.15{\pm}0.21mm$, and analyzed with $2.44{\pm}0.26mm$. If the correlation error can be defined by the length of the displacement vector in the target track is a sinusoidal breathing mode, the size of the target of the movement in response to 5 mm, 10 mm, 20 mm, respective average $0.84{\pm}0.01mm$, $0.70{\pm}0.13mm$, with $1.63{\pm}0.10mm$, if it is a variant of sudden breathing respective average $0.97{\pm}0.06mm$, $1.44{\pm}0.11mm$, and analyzed with $1.98{\pm}0.10mm$. The larger the correlation error values in both the both the respiratory form, the target error value is large. If the motion size of the target of the sine curve breathing form is greater than or equal to 20 mm, was measured at 1.5 mm or more is a recommendation value of both cyber knife manufacturer of both error value. Conclusion : There is a tendency that the correlation error value between about target error value magnitude of the target motion is large is increased, the error value becomes large in variation of rapid respiration than breathing the form of a sine curve. The more the shape of the breathing large movements regular shape of sine curves target accuracy of the tumor tracking system can be judged to be reduced. Using the algorithm of Cyber-Knife tumor tracking system, when there is a change in the sudden unpredictable respiratory due patient coughing during treatment enforcement is to stop the treatment, it is assumed to carry out the internal target validation process again, it is necessary to readjust the form of respiration. Patients under treatment is determined to be able to improve the treatment of accuracy to induce the observed form of regular breathing and put like to see the goggles monitor capable of the respiratory form of the person.

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Studies on the chemical composition of citrus fruits in Korea(I) -The chemical composition of main varieties- (한국산(韓國産) 감귤류(柑橘類)의 화학성분(化學成分)에 관(關)한 연구(硏究)(I) -주요(主要) 감귤품종별(柑橘品種別) 화학성분함량(化學成分含量)에 관(關)하여-)

  • Yang, C.B.;Park, H.;Kim, Z.U.
    • Applied Biological Chemistry
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    • v.8
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    • pp.29-37
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    • 1967
  • Citrus fruits of ten varieties grown in Chaeju island and a few other fruits for the comparison were analyzed to determined the contents of crude fat, crude fiber, total carbohydrates, macroelements and ash. Acids and sugars in fruit juices were also determined and the characteristic of neutralization of fruit juices were investigated. 1. The per cent of edible part of citrus fruits having the range of 48.5(Daingwoochi) to 72(Onju) were lower than that of other fruits. It was lower by about 8 per cent than that of the same variety produced in U.S.A. It was shown that the amount of rind per fruit might be increased in the citrus fruit grown in the low annual temperature. 2. The content of crude protein were around 1% and higher than other's. The contents of crude fat were below 0.1% in three varieties and over 0.1 in others. The contents of crude fiber were between 0.3 to 0.8% and the fruits with the high content of crude protein were inclined to have the high content of crude fiber and it was also shown that the low annual temperature was inclined to increase the amount of crude fiber per fruit. 3. The amount of total acid were from 19.5 m.e per 100 g of fresh fruit in Byongkyul to 44.2 m.e in Daingwoochi. The high percentage of titrable acid was over 90 in two sour varieties, Daingwoochi and Hakyul having pH below 3 and the high content of total acid. These two varieties were above 10 in the ratio of total acid in the edible part to the total acid in the rind(total acid in edible part/total acid in the rind). The content of combined acid was lower than that of titrable acid in the edible part and vice versa in the rind. 4. Navel was highest as 12.82% in the total sugar content and the lowest content was 4.9% of Hakyul. The contents of reducing sugar in the citrus fruits were about half of that in other fruits. The ratio of total sugar to titrable acid (sugar/acid: the grade of sweet taste) were lower than foreign products . 5. From the titration curves of fruit juices the characteristic of neutralization of juices could be grouped in three types, and other values, that is, pH, the content of total acid, the percentage of combined acid, the ratio of total acids in edible part and rind, the content of sugar, and the grade of sweet taste were also devided into the same three categories. 6. The contents of macroelements were different along to the each part of fruit. The content, in the seed were high and the ones in the rind were low. The contents of each element were in the order of $K_2O>N>P_2O_5{\gtrless}CaO{\gtrless}MgO$ in the edible part, $K_2O>N>CaO>P_2O_5{\gtrless}MgO$ in the rind, $N>K_2O>P_2O_5>CaO>MgO$ in the seed. The content of potassium was especially high in Marumeru and Hakyul and the content of calcium in citrus fruit was higher than others.

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Diagnostic Usefulness of Serum Level of Cyfra 21-1, SCC Antigen and CEA in Lung Cancer (폐암에서 혈중 Cyfra 21-1, SCC 항원 및 CEA의 진단적 유용성)

  • Kim, Kyoung-Ah;Lee, Me-Hwa;Koh, Youn-Suck;Kim, Seon-Hee;Lim, Chae-Man;Lee, Sang-Do;Kim, Woo-Sung;Kim, Dong-Soon;Kim, Won-Dong;Moon, Dae-Hyuk
    • Tuberculosis and Respiratory Diseases
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    • v.42 no.6
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    • pp.846-854
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    • 1995
  • Background: Cytokeratin 19 is a subunit of cytokeratin intermediate filament expressed in simple epithelia such as respiratory epithelial cells and their malignant counterparts. An immunoradiometric assay is available to detect a fragment of the cytokeratin, referred to as Cyfra 21-1 in the serum. This study was conducted to evaluate the clinical utility of this new marker in the diagnosis of lung cancer compared with established markers of squamous cell carcinoma antigen (SCC Ag) and carcino-embryonic antigen(CEA). In addition, we compared the diagnostic sensitivity and specificity of Cyfra 21-1 with those of SCC Ag in squamous cell carcinoma of the lung. We also measured the level of Cyfra 21-1 in the different stages of squamous cell carcinoma of the lung. Method: We measured Cyfra 21-1(ELSA-CYFRA 21-1), SCC Ag(ABBOTT SCC RIABEAD) and CEA(ELSA2-CEA) in 79 patients with primary lung cancer and in 78 persons as a comparison group including 32 patients with pulmonary tuberculosis, 23 patients with benign lung disease and 23 cases with healthy individual. Cyfra 21-1 is measured by a solid-phase immunoradiometric assay(CIS Bio International, France) based on the two-site sandwich method. SCC Ag is measured by a radioimmunoassay(Abbott Laboratories, USA). CEA is measured by a immunoradiometric assay(CIS Bio International, France). All data were expressed as the mean$\pm$standard deviation. Results: 1) The mean value of Cyfra 21-1 was $18.38{\pm}3.65\;ng/mL$ in the lung cancer and $1.l6{\pm}0.53\;ng/mL$ in the comparison group(p<0.0001). SCC Ag was $3.53{\pm}6.06\;ng/mL$ in the lung cancer and $1.19{\pm}0.5\;ng/mL$ in the comparison group(p<0.01). CEA was $35.03{\pm}13.9\;ng/mL$ in the lung cancer and $2.89{\pm}1.01\;ng/mL$ in the comparison group(p<0.0001). 2) Cyfra 21-1 level in squamous cell carcinoma($31.52{\pm}40.13\;ng/mL$) was higher than that in adenocarcinoma($2.41{\pm}1.34\;ng/mL$)(p<0.0001) and small cell carcinoma($2.15{\pm}2.05\;ng/mL$)(p=0.007). SCC Ag level in squamous cell carcinoma($5.1{\pm}7.68\;ng/mL$) was higher than that in adenocarcinoma($1.36{\pm}0.69\;ng/mL$)(p=0.009) and small cell carcinoma($1.1{\pm}0.24\;ng/mL$) (p=0.024). 3) The level of Cyfra 21-1 was not correlated with the progression of stage in squamous cell carcinoma of the lung. 4) Using the cut-off value of 3.3ng/mL, the diagnostic sensitivity of Cyfra 21-1 was 83% in squamous cell carcinoma, 22% in adenocarcinoma and 17% in small cell carcinoma. The sensitivity of SCC Ag and CEA were 39% and 20%, respectively in squamous cell carcinoma, 11% and 39% in adenocarcinoma, and 0% and 33% in small cell carcinoma. 5) Comparison of the receiver operating characteristics curves(ROC curve) for Cyfra 21-1, SCC Ag and CEA revealed that Cyfra 21-1 showed highest diagnostic sensitivity among them in the diagnosis of lung cancer. Conclusion: Cyfra 21-1 is thought to be a better tumor marker for the diagnosis of lung cancer than SCC Ag and CEA, especially in squamous cell carcinoma of the lung.

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