1.

論文

論文
鳥羽, 陽 ; 本間, 千春 ; 宇於崎, 和香 ; Chuesaard, Thanyarat ; 唐, 寧 ; 早川, 和一
出版情報: 分析化学 = Japan analyst.  63  pp.23-29,  2014-01-01.  日本分析化学会 = The Japan Society for Analytical Chemistry
URL: http://hdl.handle.net/2297/44506
概要: A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in cigarette mainstream and sidestream smoke particulates. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with six perdeuterated PAHs as internal standards. The smoke filter samples obtained from 3 brands of cigarettes using standardized smoking conditions were extracted with dichloromethane, and then treated with tandem solid phase extraction cartridges (Silica and Neutral Alumina). The limits of detection ranged from 0.24 to 2.2 pg, and were more sensitive than those by GC-MS. The analytes were quantified by using the internal standards, and the developed method achieved sufficient reproducibility and accuracy. The PAH levels in mainstream and sidestream smoke from 3 cigarette brands were in the range of 0.2 – 305 ng cigarette−1 and 26.4 – 6160 ng cigarette−1, respectively. The total PAH content in sidestream smoke was more than 10 times higher compared with that of mainstream smoke. This method should be useful as an optional analytical method to quantify PAHs in cigarette smoke particulates. 続きを見る
2.

論文

論文
松永, 明信 ; 山本, 敦 ; 水上, 英一 ; 早川, 和一 ; 宮崎, 元一
出版情報: 衛生化学 = Eisei kagaku.  34  pp.70-74,  1988-01-01.  日本薬学会 = The Pharmaceutical Society of Japan
URL: http://hdl.handle.net/2297/44933
概要: A high-performance liquid chromatographic method using post column reaction system was established for the determination of polyphosphates (PP). Linear polyphosphates with the range of polymerization from 2 to 9 (P2-P9) could be separated on an anion exchange column, TSK GEL DEAE-5PW (Toyo Soda), with 0.01 M HNO3 containing NaNO3 as a mobile phase at flow rate of 1.0 ml/min, with a linear gradient in NaNO3 concentration at one hour intervals. PP were detected as the decrease of absorbance at 500 nm of ferric-sulfosalicylate complex by means of an on-line post column reaction at room temperature, with 0.5 mM FeCl3 containing 2.5 mM sulfosalicylic acid as reaction reagent at flow rate of 0.5 ml/min. The proposed method was applied to the analysis of 30 different commercial products of soft drinks. The pretreatment only necessary after mixing the sample with an equal volume of 0.01 M HNO3 was filtration through 0.45 μm pore size filter. P2-P6 (total 0.231 g/kg) and P2-P4 (0.070 g/kg) were found from 2 kinds of the samples, respectively. The determination limit was 0.02 m mol/kg for all of the PP. 続きを見る
3.

論文

論文
早川, 和一
出版情報: 藥學雜誌 = Journal of the Pharmaceutical Society of Japan.  114  pp.669-680,  1994-01-01.  日本薬学会 = The Pharmaceutical Society of Japan
URL: http://hdl.handle.net/2297/44501
概要: Recent studies on the three new photometric detection in the liquid chromatographic methods have been reviewed. The detector and systems based on these detection theories and their applications to several fields have been also described. Differential photometric detection using UV-visible absorbing eluents enabled us to examine the retention and detection mechanism of sample and eluent ions in ion exchange chromatography. Photometric detection in ion chromatography determined transparent ionic compounds using indirect photometric detection mode of this theory. This method was useful for many samples such as environmental water and foods. Polarized photometric detection method has been developed by introducing two polarizers on either side of the UV-visible absorbance detector flow cell. The monitor determined optically active compounds as the change in absorbance. This method was applied for determining food additives such as sugars and organic compounds. A HPLC system with a chemiluminescence detector has been developed for the determination of trace levels of mutagenic nitroarenes such as 1, 3-, 1, 6-, 1, 8-dinitropyrenes and 1-nitropyrene. Utilizing this system, their exhaust from vehicles and behavior in air were examined in detail. This system was also used for determining methamphetamines in abuser urine and hair. 続きを見る
4.

論文

論文
村橋, 毅 ; 早川, 和一 ; 岩本, 侑子 ; 宮崎, 元一
出版情報: 分析化学 = Japan analyst.  43  pp.1017-1020,  1994-11-05.  The Japan Society for Analytical Chemistry = 日本分析化学会
URL: http://hdl.handle.net/2297/24842
概要: 金沢大学医薬保健研究域薬学系<br />A simultaneous determination method for polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAH s) in airborne particulates was developed. Airborne particulates were extracted with benzene/ethanol, cleaned up by liquid-liquid partition, refluxed in the presence of NaSH and then the resultant solution was injected into an HPLC system. The system was hybridized into two systems with different optimum conditions for PAHs and NPAHs by introducing a switching valve and a mini separation column. Mobile phases were acetonitrile/water (75 : 25) for PAHs, and acetonitrile/imidazole HClO_4 buffer (1 : 1) for NPAHs and the postcolumn reagent solution for NPAHs was an acetonitrile solution containing bis(2,4,6-trichlorophenyl)oxalate and H_2O_2. By this method, four NPAHs (1,3-, 1,6-, 1,8-dinitropyrenes and 1-nitropyrene) and eight PAHs (fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene and coronene) in sub-milligram quantities of airborne particulates were determined chemilumigenically and fluorogenically, respectively using 2-fluoro-7-nitrofluorene as an internal standard within sixty minutes. 続きを見る
5.

論文

論文
早川, 和一 ; Hayakawa, Kazuichi
出版情報: 平成15(2003)年度科学研究費補助金 基盤研究(B) 研究成果報告書 = 2003 Fiscal Year Final Research Report.  2002-2003  pp.9p.-,  2004-03-01.  金沢大学自然科学研究科
URL: http://hdl.handle.net/2297/48775
概要: ディーゼル排出粉塵(DEPE)及びその構成成分の一つである多環芳香族炭化水素(PAH)類の内分泌攪乱作用について,昨年度はエストロゲン様/抗エストロゲン活性を明らかにした.今年度はDEPE及びPAHのアンドロゲン様活性/抗アンドロゲン活性に ついて検討した。DEPEをヒトPC3/AR培養細胞を用いたルシフェラーゼレポーターアッセイに適用した結果,アンドロゲン様活性は認められなかったが,抗アンドロゲン活性が観察された。DEPEに含まれるいくつかの4,5環PAHは,強い抗アンドロゲン活性を示した。また,DEPE及び4,5環PAHはいずれも,ヒトのアリルヒドロカーボンレセプター(AhR)のアゴニストであった。以上の結果から,DEPEは抗アンドロゲン活性を示し,その一部はDEPEに含まれるPAHに由来することがわかった。更に,酵母two-hybrid法を用いた結果,DEPE及びいくつかのニトロ多環芳香族炭化水素が抗アンドロゲン活性を示した。次に,分析対象のモノヒドロキシ多環芳香族炭化水素(OHPAH)の数を増加させるために,逆相HPLC/蛍光検出法の条件を改良した。また,ヒト尿試料に適用可能とするために,OHPAHの抱合体も加水分解してOHPAHと合わせて定量する前処理方法を開発した。その結果,喫煙者は非喫煙者に比較して尿中2-ヒドロキシフルオレン濃度が有為に高く,1-ヒドロキシピレンより有効な喫煙指標となることがわかった。また,2〜4環の複数のOHPAHを同時分析した結果,タイ人は日本人に比較して尿中の各種OHPAH濃度が高く,室内で使用する薪燃料由来の煙の影響が大きいと推定された。このように,開発したOHPAH分析法は,ガス状及び粒子状のいずれのPAHの代謝物も分析対象としており,異なる多様なPAH発生源にも対応できることから,ヒトのPAH個人曝露量評価法として有用なことがわかった。<br />Last year, both estrogenic and antiestrogenic actions of diesel exhaust particulate(DEPE) and polycyclic aromatic hydrocarbon(PAH), which was one of the constituent of DEPE, were clarified. This year, both androgenic and antiandrogenic activities of DEPE and PAH were examined. By applying DEPE to the luciferase reporter gene assay in human PC3/AR culture cells, DEPE did not show androgenic activity but antiestrogenic activity. Several PAHs having 4 or 5 rings, which are included in DEPE, showed strong antiandrogenic activity. Both DEPE and PAHs having 4 or 5 rings, were also agonists of human allyl hydrocarbon receptor(AhR). These results suggested that DEPE showed antiandrogenic activity and that a part of this activity was derived from PAHs which were included in DEPE. In addition, several nitropolycyclic aromatic hydrocarbons showed aniandorgenic activity in the yeast two-hybrid assay. Next, to increase the number of monohydroxy polycyelic aromatic hydrocarbons(OHPAH) as analytes, conditions of our HPLC/fluorimetric detection method were modified. And, to anayze both urinary OHPAHs and their conjugates, the pretreatment method including hydrolysis of the conjugates was developed. As the result, the urinary concentration of 2-hydroxyfluorene in smokers' urine samples was higher than that in nonsmokers', and it was proven that 2-hydroxyfluorene was a more effective biomarker for smoking than 1-hydroxypyrene. Urinary OHPAH concentrations of Thai subjects were higher than those of Japanese. As a possible reason for this, the smoke of the firewood fuel used in the indoor of Thai house was considered.<br />研究課題/領域番号:14370728, 研究期間(年度):2002–2003<br />出典:「多環芳香族炭化水素とその代謝物の内分泌撹乱作用とその測定法に関する研究」研究成果報告書 課題番号14370728 (KAKEN:科学研究費助成事業データベース(国立情報学研究所))   本文データは著者版報告書より作成 続きを見る
6.

論文

論文
早川, 和一 ; Hayakawa, Kazuichi
出版情報: 平成7(1995)年度 科学研究費補助金 試験研究(B) 研究成果報告書 = 1995 Fiscal Year Final Research Report.  1994-1995  pp.8p.-,  1996-03-01.  金沢大学大学院自然科学研究科
URL: http://hdl.handle.net/2297/48779
概要: (1)大気粉じんから変異原物質を抽出するために使用されている様々な有機溶媒の中から,ニトロアレーン分析法とAmes法の併用に最適な抽出溶媒の検索をおこなった.1,3-, 1,6-, 1,8-ジニトロピレン(DNP),1-ニトロピレン(NP) 及び直接変異原性物質の抽出効率はベンゼン-エタノール(3:1),アセトニトリル,エタノール,メタノールの順で高く,毒性を考慮するとこれらの中ではエタノールが最も適していると考えられた. (2)基本ニトロアレーン分析計では試料の前処理として必要な還元操作を,分析システムに亜鉛を充填した還元用カラムを導入することにより省略した.また,分離度を向上させるため,試料を還元後,最も還元成績体の濃度が高い部分をスイッチングバルブでハードカッティングして,分析カラムに導入した.これによって簡単な前処理のみで大気粉じん中の1,3-, 1,6-, 1,8-DNP及び1-NPが定量可能となった. (3)ニトロアレーン分析法の前処理操作では直接変異原性ニトロアレーンと同時に間接変異原性多環芳香族炭化水素(PAH)も定量化に抽出される.この試料をニトロアレーン分析計とPAH分析のための蛍光検出HPLCシステムをスイッチングバルブで併合したシステムに適用することで,両者の同時分析が可能となった.その結果,上記の4種ニトロアレーンに加えて8種PAHも1時間以内に定量可能となった. (4)大気中で2次生成することが知られている2-, 4-NP,2-ニトロフルオランテン,6-ニトロクリセンと1-NPを同時に分析するため,基本ニトロアレーン分析システムに妨害物質を除去するための精製用ODSカラム,還元を自動化する亜鉛充填カラムと分離・検出を改善する濃縮用ODSカラムを導入した.本法によって測定した金沢市市街地大気中の上記化合物濃度は10^<-12>-10^<-16>molm^<-3>の範囲にあった.<br />(1) Both the nitroarene analyzer and the Ames test are necessary in the study on mutagenic nitroarenes. For the simultaneous use of these two methods, several solvent systems were tested to extract 1,3-dinitropyrene (1,3-DNP), 1,6-DNP,1,8-DNP and 1-nitropyrene (1-NP) as well as directacting mutagenic activity from airborne particulates. Benzene-ethanol, acetonitrile, ethanol and methanol gave the high efficiencies. Considering toxicities, ethanol seemed to be the best solvent.(2) Although the nitroarene analyzer determined trace levels of 1,3-, 1,6-and 1,8-DNPs and 1-NP in extracts from a few mg of airborne particulates, the reduction of nitroarenes to corresponding aminoarenes was required before injection. To remove this tedious treatment, a reducer column packed with zinc/glass beads was on-line introduced into the system. Considering the better resolution of aminoarenes, both the reducer column and a switching valve equipped with a heart-cutting loop were introduced just before the ODS separation column. This system could determine the above four compounds in extracts from airborne particulatates without pre-column reduction.(3) In the method, not only nitroarenes but also polycyclic aromatic hydrocarbons (PAHs) were quantitatively extracted from airborne partculates. To determine them simultaneously, both the nitroarene analyzer and a conventional high-performance liquid chromatograph with a fluorescence detector were combined using a switching valve. After the reduced sample solution was injected, four nitroarenes and eight PAHs were separately determined in the two different lines in 1h with high sensitivities.(4) Several mutagenic nitroarenes such as 2-, 4-NPs, 2-nitrofluoranthene and 6-nitrochrycene were formed in air in the presence of NOx. To determine these compounds, a reducer column packed with zinc/glass beads and two ODS columns, one for the clean-up and the other for the concentration, were introduced into the nitroarene analyzer. By the system, the above four compounds were detected in air. The fact that their ratios to 1,3-, 1,6-, 1,8-DNPs and 1-NP in rural air were larger than those in urban air suggested the formation of those compounds during the transportation. However, their mutagenic contributions were not large.<br />研究課題/領域番号:06557121, 研究期間(年度):1994–1995<br />出典:「ニトロアレーン分析計の試作」研究成果報告書 課題番号06557121(KAKEN:科学研究費助成事業データベース(国立情報学研究所))   本文データは著者版報告書より作成 続きを見る