WO2013006000A2 - Method for detecting breast cancer using respiratory gas - Google Patents

Method for detecting breast cancer using respiratory gas Download PDF

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WO2013006000A2
WO2013006000A2 PCT/KR2012/005348 KR2012005348W WO2013006000A2 WO 2013006000 A2 WO2013006000 A2 WO 2013006000A2 KR 2012005348 W KR2012005348 W KR 2012005348W WO 2013006000 A2 WO2013006000 A2 WO 2013006000A2
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breast cancer
methyl
acid
electronic nose
acethyl
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PCT/KR2012/005348
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French (fr)
Korean (ko)
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WO2013006000A3 (en
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라정찬
허재욱
김수현
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주식회사 알앤엘내츄럴
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
    • A61B5/082—Evaluation by breath analysis, e.g. determination of the chemical composition of exhaled breath
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry
    • G01N27/623—Ion mobility spectrometry combined with mass spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/574—Immunoassay; Biospecific binding assay; Materials therefor for cancer
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/574—Immunoassay; Biospecific binding assay; Materials therefor for cancer
    • G01N33/57407—Specifically defined cancers
    • G01N33/57415—Specifically defined cancers of breast

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  • the present invention relates to a method for measuring breast cancer or breast cancer progression stage using respiratory gas, and more particularly, to a method for measuring breast cancer progression or breast cancer progression through analysis of breathing gas using an electronic nose. .
  • the present invention also relates to a method for providing information for diagnosing breast cancer or breast cancer progression stage by analyzing respiratory gas using an electronic nose.
  • the electronic nose is a digitalization of the olfactory function of the human nose, and is composed of a high precision sensor corresponding to the olfactory cells of the human nose and a computer corresponding to the olfactory cortex of the human brain.
  • Conventional electronic nose was used in the food field, such as check whether the authenticity of the wine and whether the food rancidity (Korean Patent No. 10-0463677).
  • Breast cancer is a malignant tumor of the breast, and it is known to be caused by a transition from cancer cells to epithelial cells, which are the outermost cells in tissues or milk tubes that make milk (milk). Breast cancer is known to occur most frequently among women in developed countries, and Korea is the second most common cancer after stomach cancer. In addition, it is the fifth highest mortality cancer after stomach cancer, liver cancer, uterine cancer, and lung cancer.
  • the characteristics of breast cancer in Korea is that the frequency of breast cancer is relatively high in the 40's, unlike the prevalence in the 50's in the West. Therefore, a breast cancer management guideline suitable for Korea, which is different from the western breast cancer management guideline, is needed.
  • Breast cancer is a cancer that can be diagnosed early and treated early. Therefore, early diagnosis is important. Early detection of breast cancer is known to have a 10-year survival rate of about 85% or more. Therefore, in order to increase the survival of the patient, early diagnosis is the best method when the lesion range is small. Therefore, the diagnosis method is more efficient than the conventional breast cancer diagnosis methods. The development of breast cancer specific biomarkers with high sensitivity and specificity is urgently needed.
  • the present inventors have diligently tried to develop a method for effectively detecting breast cancer.
  • the respiratory gas of a breast cancer patient is measured with an electronic nose, the present inventors have confirmed that the presence of breast cancer and the progression stage of breast cancer can be effectively detected.
  • the present invention has been completed.
  • the present invention relates to a method for measuring breast cancer or breast cancer progression stage using respiratory gas, and more particularly, to a method for measuring breast cancer progression or breast cancer progression through analysis of breathing gas using an electronic nose. .
  • the present invention also relates to a method for providing information for diagnosing breast cancer or breast cancer progression stage by analyzing respiratory gas using an electronic nose.
  • the present invention comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It provides a method for measuring the progression of breast cancer or whether breast cancer comprising the step of detecting the detection of a gas containing.
  • the present invention also comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And
  • nonane tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl- 4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5 , 5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cy
  • the present invention also comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It provides a method for providing information for diagnosing whether breast cancer or breast cancer progression step comprising measuring the detection of a gas containing.
  • the present invention also comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And
  • nonane tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl- 4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5 , 5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cy
  • 1 is a result of analyzing the breathing gas of the breast cancer patient with an electronic nose.
  • the present invention in one aspect (a) analyzing the collected respiratory gas with an electronic nose;
  • the present invention relates to a method for measuring breast cancer or breast cancer progression, comprising measuring whether a gas is contained therein.
  • the present invention in another aspect (a) analyzing the collected respiratory gas with an electronic nose; And (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl -4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5, 5,5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene,
  • breast cancer patients have a difference in the smell of respiratory gases when compared to healthy people.
  • the present inventors distinguished patients from breast cancer from normal patients by selecting a volatile substance related to odor from the respiratory gas and patterning the detection degree of the volatile substance.
  • a volatile substance related to odor from the respiratory gas preferably, at least 10 volatile substances in the respiratory gases collected from the target subject and the healthy subject are selected and patterned according to the detection amount, thereby comparing the pattern of the target subject and the healthy subject to measure the presence or absence of breast cancer in the subject. It was confirmed. More preferably, 20 or more volatile substances may be selected and compared with their detection amount patterned.
  • the substance disclosed in the present invention when measuring whether the substance disclosed in the present invention is detected in the respiratory gas, it is possible to measure the presence or absence of breast cancer or the progression stage of breast cancer depending on the presence or absence of a difference in detection amount.
  • a group of 10 or more volatile substances having high discrimination among samples among the substances belonging to the mass range of 100-200 amu was selected and used (see Examples).
  • the present invention in another aspect (a) analyzing the collected respiratory gas with an electronic nose;
  • the present invention relates to a method for providing information for diagnosing breast cancer or breast cancer progression, including measuring whether gas is detected.
  • the present invention (a) analyzing the collected respiratory gas with an electronic nose; And (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl -4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5, 5,5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene,
  • the respiratory gas of the breast cancer and normal people are collected and analyzed through an electronic nose, the normal person, early stage breast cancer patients of stage 0 breast cancer, patients with breast cancer tumors only, patients with other cancers (thyroid cancer) together with breast cancer
  • the results showed that patients undergoing chemotherapy had different patterns of results.
  • the electronic nose is a digital representation of the nose function of the human nose, using the multi-sensor array technology to represent the specific scent or odor component and the electrochemical reactions in each sensor as an electrical signal.
  • an electronic coin Smart Nose300 (Switzerland) connected to a mass spectrometer was used.
  • the electronic nose may be characterized in that the mass spectrometer (Mass-Spectrometer) is mounted, the detection of the gas may be characterized by measuring by using a mass spectrometer mounted on the electronic nose.
  • the type of mass spectrometer is not limited.
  • measuring whether or not gas is detected means to measure not only the presence of gas but also the amount of detection amount.
  • the adsorbed sample was injected while the inlet temperature was 200 ° C.
  • the gas used was nitrogen (99.999%) and flowed at a flow rate of 230 ml per minute.
  • Data collection time was 3 minutes, purge lasted 3 minutes after analysis, and purge between samples was maintained for 3 minutes.
  • Samples were analyzed using an electronic nose (SMart Nose300, Smart Nose, Marin-Epagnier, Switzerland).
  • the electronic nose used for analysis was connected to a mass spectrometer (Quadrapole Mass Spectrometer, Balzers Instruments, Marin-Epagnier, Switzerland).
  • Volatile materials were ionized at 70 eV and passed through quadrupole mass filters for ionic materials produced for 180 seconds.
  • the materials in a specific mass range (10-200 amu) were measured in integer units and used as the number of channels.
  • Discriminant function analysis is based on the mass detection amount of molecules obtained by ionization among about 150 ion fragments generated from MS (mass), and 20-30 fragments (m / z) The group was chosen as an independent variable. Discriminant function analysis (DFA) was performed using the intensity value corresponding to the selected independent variable according to the following equation and the independent variable affecting the dependent variable was tested.
  • DF1 represents a discrimination function value
  • B0 represents a discrimination function coefficient
  • Bi represents a discrimination function coefficient
  • X represents the intensity of each fragment's amu value.
  • the discriminant function values for predicting the dependent variables are represented as discriminant funtion first score (DF1), discriminant funtion second score (DF2), and DF3.
  • DF1 and DF2 were selected based on the order of influencing the dependent variables, and the relationship between samples was mainly analyzed using these two dependent variables.
  • Discriminant function analysis by selecting 10-20 groups of variables that have the highest molecular weight (m / z) among the molecules obtained by ionization. was carried out.
  • the software used was Smart Nose tatistical analysis software.
  • a normal, early stage breast cancer patients of breast cancer stage 0 patients with breast cancer tumors only, patients with breast cancer and other cancers (thyroid cancer), patients undergoing chemotherapy
  • Respiratory gases have different patterns, which are also useful for enhancing the incompleteness, low sensitivity and specificity of early diagnostic methods, which have been pointed out as limitations of conventional breast cancer measurement.

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Abstract

The present invention relates to a method for detecting breast cancer or the progression of breast cancer using respiratory gas, and more specifically, to a method for detecting breast cancer or the progression of breast cancer by analyzing respiratory gas using an electronic nose. In addition, the present invention relates to a method for providing information on the diagnosis of breast cancer or the progression of breast cancer by analyzing respiratory gas using an electronic nose. According to the present invention, when analyzing the collected respiratory gas using an electronic nose a normal person, an early stage breast cancer patient with stage 0 breast cancer, a patient with only a breast cancer tumor, a patient with breast cancer and other cancers (thyroid cancer), and a patient under anticancer therapy show different patterns, respectively, the present invention is useful when early diagnostic methods are not adequate and to enhance sensitivity and specificity which are the limitations of conventional breast cancer detection

Description

호흡가스를 이용한 유방암의 측정방법Method of measuring breast cancer using respiratory gas
본 발명은 호흡가스를 이용하여 유방암 여부 또는 유방암의 진행단계를 측정하는 방법에 관한 것으로, 더욱 자세하게는 전자코를 이용한 호흡가스의 분석을 통해 유방암 여부 또는 유방암의 진행단계를 측정하는 방법에 관한 것이다.The present invention relates to a method for measuring breast cancer or breast cancer progression stage using respiratory gas, and more particularly, to a method for measuring breast cancer progression or breast cancer progression through analysis of breathing gas using an electronic nose. .
또한, 본 발명은 전자코를 이용한 호흡가스의 분석을 통해 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법에 관한 것이다. The present invention also relates to a method for providing information for diagnosing breast cancer or breast cancer progression stage by analyzing respiratory gas using an electronic nose.
전자코는 인간 코의 후각 기능을 디지털화한 것으로, 사람 코의 후각세포에 해당하는 초정밀 센서와 사람 뇌의 후각피질에 해당하는 컴퓨터로 구성되어 있다. 종래 전자코는 포도주의 진품 여부 확인 및 식품의 산패 여부 확인 (대한민국 등록특허 제 10-0463677호) 등 식품 분야에 국한되어 사용되었다.The electronic nose is a digitalization of the olfactory function of the human nose, and is composed of a high precision sensor corresponding to the olfactory cells of the human nose and a computer corresponding to the olfactory cortex of the human brain. Conventional electronic nose was used in the food field, such as check whether the authenticity of the wine and whether the food rancidity (Korean Patent No. 10-0463677).
유방암은 유방에 생기는 악성 종양을 말하며, 대부분 유즙(모유)를 만드는 조직이나 유즙이 밖으로 나오는 관에서 가장 바깥쪽 세포인 상피세포에서 암세포로의 변이가 생겨 발생하는 것으로 알려져 있다. 유방암은 선진국 여성들에게 가장 많이 발생하는 것으로 알려져 있으며, 우리나라의 경우 위암 다음으로 많은 암이다. 또한, 위암, 간암, 자궁암, 폐암에 이어 다섯 번째로 사망률이 높은 암으로 서양에서와 마찬가지로 빈도가 매년 증가하는 추세이다.Breast cancer is a malignant tumor of the breast, and it is known to be caused by a transition from cancer cells to epithelial cells, which are the outermost cells in tissues or milk tubes that make milk (milk). Breast cancer is known to occur most frequently among women in developed countries, and Korea is the second most common cancer after stomach cancer. In addition, it is the fifth highest mortality cancer after stomach cancer, liver cancer, uterine cancer, and lung cancer.
이러한 유방암의 증가추세는 식생활의 변화나, 서구식 생활, 첫 월경이 어려지는 추세라든지 아이를 적게 낳고, 수유를 피하며 피임약을 사용하는 등 생활패턴의 변화에 기인할 가능성이 높다. 이와 같은 현상은 이웃 일본에서도 현저하여 일본여성에게 가장 흔한 암은 유방암이 되었으며, 우리나라도 머지않아 유방암이 자궁암을 추월하여 여성암에서 수위를 차지하리라는 추측은 그리 어렵지 않다.This increase in breast cancer is likely to be due to changes in lifestyle, such as changes in diet, Western lifestyles, the first menstrual period, or fewer births, avoiding lactation, and using birth control pills. This phenomenon is remarkable in neighboring Japan, and the most common cancer in Japanese women has become breast cancer, and it is not difficult to assume that in the near future, breast cancer will overtake uterine cancer and occupy the level in female cancer.
특히, 우리나라 유방암의 특징은 서구에서는 주로 50대에 발병하는 것과는 달리 40대에 빈도가 높아 비교적 젊은 연령층에서 유방암이 많이 발생한다는 점이다. 따라서 서구의 유방암 관리 지침과는 다른 우리나라에 맞는 유방암 관리 지침서가 필요하다.In particular, the characteristics of breast cancer in Korea is that the frequency of breast cancer is relatively high in the 40's, unlike the prevalence in the 50's in the West. Therefore, a breast cancer management guideline suitable for Korea, which is different from the western breast cancer management guideline, is needed.
유방암은 조기에 진단하여 조기에 치료하면 타 암종에 비하여 좋은 결과를 기대할 수 있는 암으로 무엇보다 조기진단이 중요하다. 유방암을 조기에 발견할 경우 10년 생존율이 약 85% 이상이라고 알려져 있으며, 또한 일부만 절제하기 때문에 유방을 보존할 수도 있다. 따라서, 환자의 생존기간을 늘이려면 병변 범위가 작을 때 조기 진단하는 것이 가장 좋은 방법이므로, 기존의 각종 유방암 진단 방법보다 효율적인 진단 방법, 즉 조기 진단이 가능하고, 대용량으로 검체를 처리할 수 있으며, 민감도 및 특이도가 높은 유방암 특이적 바이오 마커의 개발이 절실히 요구되고 있는 실정이다.Breast cancer is a cancer that can be diagnosed early and treated early. Therefore, early diagnosis is important. Early detection of breast cancer is known to have a 10-year survival rate of about 85% or more. Therefore, in order to increase the survival of the patient, early diagnosis is the best method when the lesion range is small. Therefore, the diagnosis method is more efficient than the conventional breast cancer diagnosis methods. The development of breast cancer specific biomarkers with high sensitivity and specificity is urgently needed.
이에, 본 발명자들은 유방암을 효과적으로 검출할 수 있는 방법을 개발하고자 예의 노력한 결과, 유방암 환자의 호흡가스를 전자코로 측정할 경우, 유방암 존재 여부 및 유방암의 진행단계를 효과적으로 검출할 수 있다는 것을 확인하고 본 발명을 완성하게 되었다.Accordingly, the present inventors have diligently tried to develop a method for effectively detecting breast cancer. As a result, when the respiratory gas of a breast cancer patient is measured with an electronic nose, the present inventors have confirmed that the presence of breast cancer and the progression stage of breast cancer can be effectively detected. The present invention has been completed.
발명의 요약Summary of the Invention
본 발명은 호흡가스를 이용하여 유방암 여부 또는 유방암의 진행단계를 측정하는 방법에 관한 것으로, 더욱 자세하게는 전자코를 이용한 호흡가스의 분석을 통해 유방암 여부 또는 유방암의 진행단계를 측정하는 방법에 관한 것이다. 또한, 본 발명은 전자코를 이용한 호흡가스의 분석을 통해 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법에 관한 것이다. The present invention relates to a method for measuring breast cancer or breast cancer progression stage using respiratory gas, and more particularly, to a method for measuring breast cancer progression or breast cancer progression through analysis of breathing gas using an electronic nose. . The present invention also relates to a method for providing information for diagnosing breast cancer or breast cancer progression stage by analyzing respiratory gas using an electronic nose.
상기 목적을 달성하기 위하여, 본 발명은 (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및 (b) 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene 중 어느 하나를 함유하는 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법을 제공한다. In order to achieve the above object, the present invention comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It provides a method for measuring the progression of breast cancer or whether breast cancer comprising the step of detecting the detection of a gas containing.
본 발명은 또한, (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및The present invention also comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And
(b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl-4(1H)-quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5-(1-methylethenyl)-(R)-cycolhexane, 1,2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo[e]azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene-(V4), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7-(3-oxobutylidene)oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1-azulene carbonitrile, 5-(2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene로 구성되는 군에서 선택되는 2 이상의 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법을 제공한다.(b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl- 4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5 , 5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cycolhexane, 1,2 , 4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane , 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo [e] azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene- (V4) , 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis (1,1-dimethylethyl) -2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoqui none, acetic acid, 2,6,6-trimethyl-3-methylene-7- (3-oxobutylidene) oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1 -azulene carbonitrile, 5- (2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6 Breast cancer or breast cancer comprising measuring the detection of two or more gases selected from the group consisting of -dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It provides a method of measuring the progress of the.
본 발명은 또한, (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및 (b) 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene 중 어느 하나를 함유하는 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법을 제공한다. The present invention also comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It provides a method for providing information for diagnosing whether breast cancer or breast cancer progression step comprising measuring the detection of a gas containing.
본 발명은 또한, (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및The present invention also comprises the steps of (a) analyzing the collected respiratory gas with an electronic nose; And
(b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl-4(1H)-quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5-(1-methylethenyl)-(R)-cycolhexane, 1,2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo[e]azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene-(V4), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7-(3-oxobutylidene)oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1-azulene carbonitrile, 5-(2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene로 구성되는 군에서 선택되는 2 이상의 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법을 제공한다.(b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl- 4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5 , 5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cycolhexane, 1,2 , 4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane , 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo [e] azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene- (V4) , 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis (1,1-dimethylethyl) -2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoqui none, acetic acid, 2,6,6-trimethyl-3-methylene-7- (3-oxobutylidene) oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1 -azulene carbonitrile, 5- (2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6 Breast cancer or breast cancer comprising measuring the detection of two or more gases selected from the group consisting of -dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It provides a method for providing information for diagnosing the progression of the.
도 1은 유방암 환자의 호흡가스를 전자코로 분석한 결과이다.1 is a result of analyzing the breathing gas of the breast cancer patient with an electronic nose.
발명의 상세한 설명 및 구체적인 구현예Detailed Description of the Invention and Specific Embodiments
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술 분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술 분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
본 발명은 일 관점에서 (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및The present invention in one aspect (a) analyzing the collected respiratory gas with an electronic nose; And
(b) 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene 중 어느 하나를 함유하는 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법에 관한 것이다. (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid and trichloroethylene The present invention relates to a method for measuring breast cancer or breast cancer progression, comprising measuring whether a gas is contained therein.
본 발명은 다른 관점에서 (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및 (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl-4(1H)-quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5-(1-methylethenyl)-(R)-cycolhexane, 1,2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo[e]azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene-(V4), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7-(3-oxobutylidene)oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1-azulene carbonitrile, 5-(2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene로 구성되는 군에서 선택되는 2 이상의 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법에 관한 것이다.The present invention in another aspect (a) analyzing the collected respiratory gas with an electronic nose; And (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl -4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5, 5,5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cycolhexane, 1, 2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl- dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo [e] azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene- (V4 ), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis (1,1-dimethylethyl) -2,5-cyclohexadiene-1,4-dione , 2,5-di-tert-butyl-1,4-benz oquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7- (3-oxobutylidene) oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1 -azulene carbonitrile, 5- (2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6 Breast cancer or breast cancer comprising measuring the detection of two or more gases selected from the group consisting of -dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It relates to how to measure the progress of the.
유방암 환자는 건강인의 경우와 비교하였을 때, 호흡가스의 냄새에 차이가 있다. 본 발명자들은 이러한 사실을 기반으로, 냄새와 관련된 휘발성 물질을 호흡가스에서 선택하여 해당 휘발성 물질의 검출 정도를 패턴화하여 유방암 환자와 정상인 환자를 구별하였다. 이때, 바람직하게는 검출대상인과 건강인으로부터 채취된 호흡가스 중 10개 이상의 휘발성 물질을 선택하여 검출량에 따라 패턴화하여 검출대상인과 건강인의 패턴을 비교함으로써 검출대상인의 유방암 유무를 측정할 수 있음을 확인하였다. 더욱 바람직하게는 20개 이상의 휘발성 물질을 선택하여 이들의 검출량을 패턴화한 것을 비교할 수 있다. 또한, 본 발명에서 개시하고 있는 물질이 호흡 가스에서 검출되는지 측정할 때, 검출량의 차이뿐 아니라 존재 유무에 따라 유방암 유무 또는 유방암의 진행단계를 측정할 수 있다. 본 발명의 실시예에서는 질량 범위가 100-200 amu에 속하는 물질 중 시료 간에 차별성이 높은 10 여개 이상의 휘발성 물질 그룹을 선정하여 사용하였다 (실시예 참조). Breast cancer patients have a difference in the smell of respiratory gases when compared to healthy people. Based on this fact, the present inventors distinguished patients from breast cancer from normal patients by selecting a volatile substance related to odor from the respiratory gas and patterning the detection degree of the volatile substance. In this case, preferably, at least 10 volatile substances in the respiratory gases collected from the target subject and the healthy subject are selected and patterned according to the detection amount, thereby comparing the pattern of the target subject and the healthy subject to measure the presence or absence of breast cancer in the subject. It was confirmed. More preferably, 20 or more volatile substances may be selected and compared with their detection amount patterned. In addition, when measuring whether the substance disclosed in the present invention is detected in the respiratory gas, it is possible to measure the presence or absence of breast cancer or the progression stage of breast cancer depending on the presence or absence of a difference in detection amount. In the embodiment of the present invention, a group of 10 or more volatile substances having high discrimination among samples among the substances belonging to the mass range of 100-200 amu was selected and used (see Examples).
따라서, 본 발명은 다른 관점에서 (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및 Accordingly, the present invention in another aspect (a) analyzing the collected respiratory gas with an electronic nose; And
(b) 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene 중 어느 하나를 함유하는 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법에 관한 것이다. (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid and trichloroethylene The present invention relates to a method for providing information for diagnosing breast cancer or breast cancer progression, including measuring whether gas is detected.
또한, 본 발명은 다른 관점에서 (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및 (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl-4(1H)-quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5-(1-methylethenyl)-(R)-cycolhexane, 1,2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo[e]azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene-(V4), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7-(3-oxobutylidene)oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1-azulene carbonitrile, 5-(2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene로 구성되는 군에서 선택되는 2 이상의 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법에 관한 것이다. In another aspect, the present invention (a) analyzing the collected respiratory gas with an electronic nose; And (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl -4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5, 5,5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cycolhexane, 1, 2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl- dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo [e] azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene- (V4 ), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis (1,1-dimethylethyl) -2,5-cyclohexadiene-1,4-dione , 2,5-di-tert-butyl-1,4-benz oquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7- (3-oxobutylidene) oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1 -azulene carbonitrile, 5- (2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6 Breast cancer or breast cancer comprising measuring the detection of two or more gases selected from the group consisting of -dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene It relates to a method for providing information for the diagnosis of the progression of the.
본 발명의 실시예에서는 유방암 및 정상인의 호흡가스를 채취하여 전자코를 통하여 분석한 결과, 정상인, 유방암 0기의 초기 유방암 환자, 유방암 종양만을 가지는 환자, 유방암 외 다른 암 (갑상선암)을 함께 가지는 환자, 항암치료 중인 환자가 각각 서로 다른 패턴의 결과를 가지는 것을 확인하였다.In the embodiment of the present invention, the respiratory gas of the breast cancer and normal people are collected and analyzed through an electronic nose, the normal person, early stage breast cancer patients of stage 0 breast cancer, patients with breast cancer tumors only, patients with other cancers (thyroid cancer) together with breast cancer The results showed that patients undergoing chemotherapy had different patterns of results.
전자코는 인간 코의 후각 기능을 디지털화한 것으로 Multi-sensor Array 기술을 이용하여 특정 향기 또는 냄새성분과 각각의 센서에서의 전기화학적 반응을 전기신호로 나타낸 것이다. 본 발명에서는 질량분석기와 연결된 전자코인 Smart Nose300 (Switzerland)를 사용하였다.The electronic nose is a digital representation of the nose function of the human nose, using the multi-sensor array technology to represent the specific scent or odor component and the electrochemical reactions in each sensor as an electrical signal. In the present invention, an electronic coin Smart Nose300 (Switzerland) connected to a mass spectrometer was used.
본 발명에서 전자코는 질량분석기 (Mass-Spectrometer)가 장착되어 있는 것을 특징으로 할 수 있고, 가스의 검출은 전자코에 장착된 질량분석기를 이용하여 측정하는 것을 특징으로 할 수 있다. 이때, 질량 분석기의 종류는 제한되지 않는다. In the present invention, the electronic nose may be characterized in that the mass spectrometer (Mass-Spectrometer) is mounted, the detection of the gas may be characterized by measuring by using a mass spectrometer mounted on the electronic nose. At this time, the type of mass spectrometer is not limited.
본 발명에서, "가스의 검출 여부를 측정"한다는 것은, 가스의 존재 유무뿐 아니라 검출량 정도를 측정하는 것을 포함하는 의미이다.In the present invention, "measuring whether or not gas is detected" means to measure not only the presence of gas but also the amount of detection amount.
실시예 Example
이하, 하기 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것이므로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다 Hereinafter, the present invention will be described in more detail with reference to the following examples. Since these examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.
실시예 1: 호흡가스 시료를 준비하는 단계Example 1 Preparing a Respiratory Gas Sample
건강인의 호흡가스 10가지, 유방암 환자의 호흡가스 10가지(0기암 환자 5개, 항암치료중인 환자 3개, 유방암 및 갑상선 암 환자 1개) 총 20 가지 시료를 분석하였다. 시료는 index syringe를 이용하여 100ml 포집하여 흡착시켰다.A total of 20 samples were analyzed: 10 respiratory gases from healthy individuals, 10 respiratory gases from breast cancer patients (5 stage 0 cancer patients, 3 patients undergoing chemotherapy, 1 breast cancer and thyroid cancer patients). The sample was collected by 100 ml using an index syringe and adsorbed.
실시예 2: 전자코를 이용하여 분석하는 단계 Example 2: Analyzing Using Electronic Nose
흡착된 시료를 주입구 온도가 200℃인 상태에서 주입하였다. 이 때 사용한 가스는 질소(99.999%)였으며 분당 230ml의 유속으로 흘려보냈다. 데이터 수집시간은 3분이며 분석 후 purge는 3분간 지속되었고 시료 사이에서의 purge도 3분간을 유지하였다. 시료는 전자코 (SMart Nose300, Smart Nose, Marin-Epagnier, Switzerland)로 분석하였으며 분석에 사용된 전자코는 질량분석기(Quadrapole Mass Spectrometer, Balzers Instruments, Marin-Epagnier, Switzerland)가 연결되어 있다. 휘발성 물질들은 70 eV 에서 이온화시켜 180초 동안 생성된 이온물질을 사중극자(quadrupole)질량 필터를 거친 후 특정 질량 범위(10-200amu)에 속하는 물질을 정수단위로 측정하여 channel수로 사용하였다.The adsorbed sample was injected while the inlet temperature was 200 ° C. The gas used was nitrogen (99.999%) and flowed at a flow rate of 230 ml per minute. Data collection time was 3 minutes, purge lasted 3 minutes after analysis, and purge between samples was maintained for 3 minutes. Samples were analyzed using an electronic nose (SMart Nose300, Smart Nose, Marin-Epagnier, Switzerland). The electronic nose used for analysis was connected to a mass spectrometer (Quadrapole Mass Spectrometer, Balzers Instruments, Marin-Epagnier, Switzerland). Volatile materials were ionized at 70 eV and passed through quadrupole mass filters for ionic materials produced for 180 seconds. The materials in a specific mass range (10-200 amu) were measured in integer units and used as the number of channels.
실시예 3: 전자코에 의한 판별함수 분석Example 3 Analysis of Discriminant Function by Electronic Nose
판별함수분석(DFA; discriminant function analysis)은 MS(mass)로부터 생성되는 150여개의 ion fragment 중 이온화되어 얻어진 분자들의 질량별 검출량을 기준으로 각 시료 간에 차별성이 높은 20-30 여개의 fragments (m/z)그룹을 독립변수로 선택하였다. 선택된 독립변수에 해당하는 감응도(intensity)값을 이용하여 다음의 식에 따라서 판별함수분석(DFA)을 실시하였으며 종속변수에 영향을 주는 독립변수를 검정하였다.Discriminant function analysis (DFA) is based on the mass detection amount of molecules obtained by ionization among about 150 ion fragments generated from MS (mass), and 20-30 fragments (m / z) The group was chosen as an independent variable. Discriminant function analysis (DFA) was performed using the intensity value corresponding to the selected independent variable according to the following equation and the independent variable affecting the dependent variable was tested.
DF1 = B0+B1X1+B2X2+B3X3+······ +BnXnDF1 = B0 + B1X1 + B2X2 + B3X3 + ... + BnXn
DF1는 판별함수값, B0 는 판별상수, Bi는 판별함수계수, X는 각 fragment 의 amu값에서의 intensity를 나타낸다. 이들 독립변수 중에서 종속변수를 예측할 수 있는 판별 함수값은 DF1(discriminant funtion first score), DF2(discriminant funtion second score), DF3······DFn으로 나타내었다. 여러 독립변수들 중에서 종속변수에 영향력을 주는 순서를 기준으로 DF1과 DF2를 정하였고, 주로 이 2가지의 종속변수를 이용하여 시료간의 관계를 해석하였다. 각기 다른 channel의 감응도의 세기를 matrix형태로 기록되었으며 이온화되어 얻어진 분자들 중 가장 차별성을 높게 표현하는 분자량(m/z)을 갖는 variables 그룹을 10-20개 선정하여 판별함수분석 (discriminant function analysis)을 실시하였다. 이때 사용된 소프트웨어는 Smart Nose tatistical analysis software를 사용하였다. DF1 represents a discrimination function value, B0 represents a discrimination function coefficient, Bi represents a discrimination function coefficient, and X represents the intensity of each fragment's amu value. Among these independent variables, the discriminant function values for predicting the dependent variables are represented as discriminant funtion first score (DF1), discriminant funtion second score (DF2), and DF3. Among the independent variables, DF1 and DF2 were selected based on the order of influencing the dependent variables, and the relationship between samples was mainly analyzed using these two dependent variables. Discriminant function analysis by selecting 10-20 groups of variables that have the highest molecular weight (m / z) among the molecules obtained by ionization. Was carried out. The software used was Smart Nose tatistical analysis software.
그 결과, 유방암 환자와 정상인의 패턴이 다르게 나타나는 것을 관찰할 수 있었다. 특히, 유방암 초기 단계인, 유방암 0기 환자와 정상인의 패턴이 차이를 보이는 것을 확인하였다. 더불어 유방암 종양만을 가지는 환자와 유방암 및 갑상선암 종양을 가지는 환자의 패턴 역시 다르게 나타나는 것을 알 수 있었다. 아울러 유방암 환자와 항암치료 중인 환자의 패턴 역시 다르다는 것을 확인하였다 (도 1).As a result, it was observed that the patterns of breast cancer patients and normal people were different. In particular, it was confirmed that the pattern of the stage 0 breast cancer patients and the normal person, the early stage of breast cancer shows a difference. In addition, the patterns of patients with only breast cancer tumors and those with breast and thyroid cancer tumors were also different. In addition, it was confirmed that the patterns of breast cancer patients and patients undergoing chemotherapy are also different (FIG. 1).
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시태양일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다.As described above in detail the specific parts of the present invention, it is apparent to those skilled in the art that such specific description is merely a preferred embodiment, thereby not limiting the scope of the present invention. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
본 발명에 따르면, 채취된 호흡가스를 전자코로 분석하는 경우, 정상인, 유방암 0기의 초기 유방암 환자, 유방암 종양만을 가지는 환자, 유방암 외 다른 암 (갑상선암)을 함께 가지는 환자, 항암치료 중인 환자의 호흡가스는 각각 다른 패턴을 보이게 되어, 종래 유방암 측정의 한계점으로 지적되던 조기 진단방법의 미비, 낮은 민감도 및 특이도를 증진시키는데에도 유용하다.According to the present invention, when the collected respiratory gas is analyzed by an electronic nose, a normal, early stage breast cancer patients of breast cancer stage 0, patients with breast cancer tumors only, patients with breast cancer and other cancers (thyroid cancer), patients undergoing chemotherapy Respiratory gases have different patterns, which are also useful for enhancing the incompleteness, low sensitivity and specificity of early diagnostic methods, which have been pointed out as limitations of conventional breast cancer measurement.

Claims (10)

  1. (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및(a) analyzing the collected respiratory gas with an electronic nose; And
    (b) 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene 중 어느 하나를 함유하는 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법. (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid and trichloroethylene Method for measuring the progression of breast cancer or whether breast cancer comprising the step of detecting the detection of containing gas.
  2. (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및(a) analyzing the collected respiratory gas with an electronic nose; And
    (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl-4(1H)-quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5-(1-methylethenyl)-(R)-cycolhexane, 1,2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo[e]azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene-(V4), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7-(3-oxobutylidene)oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1-azulene carbonitrile, 5-(2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene로 구성되는 군에서 선택되는 2 이상의 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법.(b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl- 4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5 , 5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cycolhexane, 1,2 , 4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane , 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo [e] azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene- (V4) , 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis (1,1-dimethylethyl) -2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoqui none, acetic acid, 2,6,6-trimethyl-3-methylene-7- (3-oxobutylidene) oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1 -azulene carbonitrile, 5- (2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6 Breast cancer or breast cancer comprising measuring the detection of two or more gases selected from the group consisting of -dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene How to measure your progress.
  3. 제2항에 있어서, (b) 단계에서 10 이상의 가스의 검출 여부를 측정하는 것을 특징으로 하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법. The method of claim 2, wherein in step (b), 10 or more gases are detected.
  4. 제 1 항 또는 제 2 항에 있어서, 상기 전자코는 질량분석기 (Mass-Spectrometer)가 장착되어 있는 것을 특징으로 하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법.The method of claim 1 or 2, wherein the electronic nose is equipped with a mass spectrometer (Mass-Spectrometer).
  5. 제 1 항 또는 제 2 항에 있어서, 상기 가스의 검출 여부는 전자코에 장착된 질량분석기를 통해 측정하는 것을 특징으로 하는 유방암 여부 또는 유방암의 진행단계를 측정하는 방법.The method of claim 1 or 2, wherein the detection of the gas is performed by a mass spectrometer mounted on an electronic nose.
  6. (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및(a) analyzing the collected respiratory gas with an electronic nose; And
    (b) 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene 중 어느 하나를 함유하는 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법. (b) any one of 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid and trichloroethylene A method for providing information for diagnosing breast cancer or a stage of breast cancer, the method comprising measuring whether a gas is contained therein.
  7. (a) 채취된 호흡가스를 전자코로 분석하는 단계; 및(a) analyzing the collected respiratory gas with an electronic nose; And
    (b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl-4(1H)-quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5,5-hexamethyl-3-(trimethylsiloxy)trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5-(1-methylethenyl)-(R)-cycolhexane, 1,2,4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane, 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo[e]azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene-(V4), 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis(1,1-dimethylethyl)-2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoquinone, acetic acid, 2,6,6-trimethyl-3-methylene-7-(3-oxobutylidene)oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1-azulene carbonitrile, 5-(2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6-dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid 및 trichloroethylene로 구성되는 군에서 선택되는 2 이상의 가스의 검출 여부를 측정하는 단계를 포함하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법.(b) nonane, tridecane, 5-methylundecane, 3-methylpentadecane, 6-methyl propane, 2-methylnonadecane, 3-methyldodecane, 4-methyloctadecane, 2-methyl-2-propanol, 2,3-dihdro-1-phenyl- 4 (1H) -quinazolinone, 1-phenyl-ethanone, heptanal, isopropylmyristate, cyclopropane, ethylidene, 1,4-pentadiene, 1,3-butadiene, cyclotetrasiloxane, octamethyl-3-ethoxy-1,1,1,5,5 , 5-hexamethyl-3- (trimethylsiloxy) trisiolxane, benzoic acid, 4-methyl-2-trimethylsiloxy-trimethylsily ester D-limonene, 1-methyl-5- (1-methylethenyl)-(R) -cycolhexane, 1,2 , 4,5-tetramethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, tridecane, dodecane, undecane, dodecane, 2,7,10-triethyl-dodecane , 2,6,11-triethyl-tridecane, tetradecane, tridecane, pentadecane, (+)-longifolene, 1H-cyclo [e] azulene, decahydro-1,1,7-trimethyl-4-methylene, longifolene- (V4) , 2-hexyl-1-octanol, 1-octanol, 2-butyl-trifluoroacetic acid, n-octadecyl ester, 2,6-bis (1,1-dimethylethyl) -2,5-cyclohexadiene-1,4-dione, 2,5-di-tert-butyl-1,4-benzoqui none, acetic acid, 2,6,6-trimethyl-3-methylene-7- (3-oxobutylidene) oxepan-2-yl ester, 3,3-dimethylpentane, 2-amino-5-isopropyl-8-methyl-1 -azulene carbonitrile, 5- (2-methylpropyl) nonane, 2,3,4-trimethyldecane, 6-ethyl-3-octylester 2-trifluoromethybenzoic acid, 4-methyl-1,3-benzenediamine, 3-acethyl-2,6 Breast cancer or breast cancer comprising measuring the detection of two or more gases selected from the group consisting of -dimethoxypyridine, 2-acethyl-6-methoxypyridine, 2-amino-3-methylbenzoic acid, 2-aminophenylacethic acid, and trichloroethylene To provide information for diagnosing the progress of the procedure.
  8. 제7항에 있어서, (b) 단계에서 10 이상의 가스의 검출 여부를 측정하는 것을 특징으로 하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법.The method of claim 7, wherein in step (b), 10 or more gas is detected.
  9. 제 6 항 또는 제 7 항에 있어서, 상기 전자코는 질량분석기 (Mass-Spectrometer)가 장착되어 있는 것을 특징으로 하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법.8. The method of claim 6 or 7, wherein the electronic nose is equipped with a mass spectrometer (Mass-Spectrometer).
  10. 제 6 항 또는 제 7 항에 있어서, 상기 가스의 검출 여부는 전자코에 장착된 질량분석기를 통해 측정하는 것을 특징으로 하는 유방암 여부 또는 유방암의 진행단계 진단을 위한 정보를 제공하는 방법.The method of claim 6 or 7, wherein the detection of the gas is performed by using a mass spectrometer mounted on the electronic nose.
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