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宮崎元一,早川和一共著
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研究代表者 早川和一
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研究代表者 早川和一
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研究代表者 早川和一
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研究代表者 早川和一
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Hayakawa, Kazuichi ; Miyoshi, Yasuko ; Kurimoto, Hiroaki ; Matzushima, Yuko ; Takayama, Nariaki ; Tanaka, Seishi ; Miyazaki, Motoichi ; 早川, 和一 ; 三好, 裕子 ; 栗本, 博昭 ; 松島, 優子 ; 高山, 成明 ; 田中, 星司 ; 宮崎, 元一
概要:
金沢大学理工研究域自然システム学系<br />A HPLC determination method for methamphetamine (MA) and its metabolites in the urine samples of
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abusers has been developed. MA, amphetamine (AP), norephedrine (NE), p-hydroxymethamphetamine (pOHMA), p-hydoroxyamphetamine (pOHAP) and an internal standard, namely β-phenylethylamine (PEA) were derivatized with dansyl chloride. They were separated on a reversed phase column with gradient elution using an acetonitrile/tetrahydrofuran/imidazole buffer mobile phase and chemilumigenically determined using bis(2, 4, 6-trichlorophenyl)-oxalate/hydrogen peroxide as post column reagents. The lower determination limits were as low as 1×10-14-3×10-14mol. AP, NE, pOHAP and PEA were derivatized with naphthalene-2, 3-dicarboxaldehyde, and were separated on a reversed phase column using an acetonitrile/imidazole buffer mobile phase and chemilumigenically determined. The lower determination limits were 3×10-16-1.5×10-15mol. Enzymatic hydrolysis of glucuronides of pOHMA (pOHMAG) and pOHAP (pOHAPG) allowed them to be determined as pOHMA and pOHAP, respectively. After adjusting the pH of the urine samples to 10.5 and adding PEA, all metabolites except glucuronides were extracted quantitatively into chloroform-isopropanol (3 : 1). Utilizing the two methods, MA and all metabolites were determined in urine samples of MA abusers. The tendency, in order of decreasing concentration was : [MA]>[A]>[pOHMAG]>[pOHMA]>[NE]>[pOHAPG]>[pOHAP]. Although ephedrine (EP) was detected in several samples, it was not considered to be a metabolite of MA but rather a component derived from cough medicine.
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山本, 敦 ; 早川, 和一 ; Yamamoto, Atsushi ; Hayakawa, Kazuichi
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金沢大学理工研究域自然システム学系
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後藤, 純雄 ; 峯木, 茂 ; 杉田, 和俊 ; 遠藤, 治 ; 村山, 留美子 ; 内山, 巌雄 ; 田中, 基裕 ; 早川, 和一 ; Goto, Sumio ; Mineki, Shigeru ; Sugita, Kazutoshi ; Endo, Osamu ; Murayama, Rumiko ; Uchiyama, Iwao ; Tanaka, Motohiro ; Hayakawa, Kazuichi
概要:
金沢大学理工研究域自然システム学系<br />ナホトカ号から流出し日本海沿岸に漂着した重油の汚染状況を把握するための調査研究の一環として, 平成9年1月16日に採取した漂着重油, ナホトカ号船首部分の重油および市販C重油中に含まれる多環芳香
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族炭化水素 (PAH) の分析及び抽出物の変異原性を測定した。その結果, 漂着重油のベンゾ (a) ピレン (BaP) 含有量は1984年に採取された東京都市部の土砂51試料の平均値の約1/4であることやその変異原比活性は同土砂の約4倍であることなどを認めた。<br />As a part of research studies on the pollution at heavy-oil coated parts of the Sea of Japan coastline, resulting from the wrecked Russian tanker Nakhodka on Jan. 2, the following experiments were performed using three heavy oil samples. Polycyclic aromatic hydrocarbons (PAH) were analyzed by HPLC in the heavy oil that washed ashore, which was collected at Mikuni-cho in Fukui Prefecture on Jan. 16, 1997, heavy oil in the oil compartment of the bow of the tanker, and commercial heavy oil (class C) .Mutagenicities of the extracts of these oil samples were also measured. The amount of benzo (a) pyrene (BaP) contained in the heavy oil that washed ashore was about a quarter of the average in 51 soil extracted samples, which were collected at an urban area in Tokyo in 1984, and mutagenicity of the extract from the oil was about 4-fold higher than the average in the extracts from the soil samples.
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早川, 和一 ; Hayakawa, Kazuichi
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早川, 和一 ; 山本 , 敦 ; 宮崎, 元一 ; Hayakawa, Kazuichi ; Yamamoto, Atsushi ; Miyazaki, Motoichi
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早川, 和一 ; 宮崎, 元一 ; Hayakawa, Kazuichi ; Miyazaki, Motoichi
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早川, 和一 ; 木津, 良一 ; 安藤, 京子 ; 村橋, 毅 ; 東, 成見 ; 山本, 茂樹 ; 長谷川, 幸司 ; 中浜, 慶子 ; 山下, 克美 ; 松本, 健 ; 後藤, 純雄
概要:
「ナホトカ号」から抜き取った重油, 環境試料 (大気, 漂着重油, 海水) 中の芳香族成分をGC/MS, 蛍光検出HPLCで定着した。重油からはベンゼン, トルエン, エチルベンゼン, キシレン, ナフタレン, アセナフテン, フルオレン,
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アントラセン, フルオランテン, ピレン, ベンツ [a] アントラセン, クリセン, ベンゾ [b] フルオランテン, ベンゾ [k] フルオランテン, ベンゾ [a] ピレン, ジベンツ [a, h] アントラセン, ベンゾ [ghi] ペリレンが検出された。 大気中ベンゼン, トルエン, キシレン, ナフタレン濃度は有毒なレベルより遥かに低かった。しかし, モデル実験から重油流出直後はベンゼン, トルエン, キシレン, ナフタレン濃度は高いことが推定された。漂着重油中のナフタレン濃度は低下傾向が認められたが, ピレン, ベンゾ [a] ピレン濃度はほとんど同じであった。ナフタレンの減少は揮散のためと考えられた。また, 海岸砂中の多環芳香族炭化水素類の組成は漂着重油中のそれと類似していた。ベンゾ [a] ピレンの海水中濃度は低下傾向を示した。 重油の変異原性, DNA損傷についても調べた。重油はSalmonella typhimurium TA98及びTA100株に対し間接変異原性を示した。また, 重油で処理するとヒトFL細胞中でp53遺伝子を活性化させることから, DNA損傷を引き起こすことが明らかとなった。 Aromatic hydrocarbons in the oil spilled from“the Nakhodka”and in the environmental samples including air, reached oil and sea water were determined by gas chromatography/mass spectrometric detection and high-performance liquid chromatography/fluorescence detection. Aromatic hydrocarbons determined in the oil were as follows: benzene, toluene, ethylbenzene, xylenes, naphthalene, acenaphthene, fluorene, anthracene, fluoranthene, pyrene, benz [a] anthracene, chrysene, benzo [b] fluoranthene, benzo- [k] fluoranthene, benzo [a] pyrene, dibenz [a, h] anthracene and benzo [ghi] perylene. Concentrations of benzene, toluene, xylenes and naphthalene in the air collected at contaminated seashores were much lower than their toxic levels. However, a model experiment suggested that their concentrations in the air might be higher just after the oil spill. Although the naphthalene concentration in the reached oil samples tended to decrease with time, pyrene and benzo [a] pyrene concentrations were relatively constant. The decrease in naphthalene concentration in the reached oil samples was considered to be due to vaporization. Benzo [a] pyrene concentrations in sea water tended to decrease with time. The mutagenicity and DNA damage of the oil were assayed. The oil showed indirectacting mutagenicity in the Salmonella typhimurium TA98 and TA100 strains in the presence of S9 mix. Production of p53 protein was enhanced in human FL cells after the treatment with the oil, indicating that the oil caused DNA damage.
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早川, 和一 ; 今泉, 範子
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今成, 登志男 ; 大久保, 登 ; 早川, 和一 ; 宮崎, 元一
概要:
生体試料中の金属を電気透析試料調製器によって陽イオンとして直接抽出する方法(A法)とEDTA-金属錯体として陰イオンとして抽出する方法(B法)について条件の検討を行った. A法の条件は泳動液0.05N酢酸,電流密度15mA/cm2,抽出時間
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(20～40)分,B法の条件は泳動液0.05N水酸化アンモニウム-1m M EDTA,電流密度20mA/cm2,抽出時問(20～40)分であった.A法では鉄(III),銅(II)の回収率80%,亜鉛(II)の回収率は90%,一方B法については鉄(III),亜鉛(II)の回収率100%,銅(II)の回収率は95%であった.たん白質として牛血清アルブミン,電解質として塩化ナトリウムの共存の影響を調べた後,B法を血しょう中のアルブミン結合亜鉛の分析に応用した. The extraction of metals from biological materials by an electrodialytic sample preparator was studied. Two procedures are proposed in this method : one depends on the extraction of metals as cationic ions (Mode A) and the other depends on the extraction of metal-EDTA complexes as anionic ions (Mode B). The basic conditions for Mode A are : carrier solution; 0.05 N CH3COOH, current density; 15 mA/cm2, extraction time; (2040) min. The conditions for Mode B are : carrier solution; 0.05 N NH4OH-1 mM EDTA, current density; 20 mA/cm2 and extraction time; (2040)min. The recoveries of Fe(III), Cu(II) and Zn(II) in Mode A were 90, 80 and 90%, and in Mode B the recoveries were 100, 95 and 100% respectively. The effects of electrolytes and proteins on the extraction of metals were examined, and the application of Mode B for the determination of albumin bound zinc in human plasma was carried out as follows : the supernatant containing albumin bound zinc was obtained by polyethylene glycol treatment and subjected to electrodialysis for 40 min according to the conditions described in Mode B. Albumin bound zinc in the extract was determined by atomic absorption spectrometry (AAS). Total plasma zinc was measured according to direct dilution method by AAS and α2-macroglobulin bound zinc was obtained by the difference.
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木津, 良一 ; 安藤, 京子 ; 早川, 和一
概要:
The Russian tanker Nakhodka met a hull-broken accident in sailing in the Sea of Japan on January 2, 1997, releasing approximately 6200 kl of heavy oil into the Sea of Japan. The spilled oil was driven by the prevailing winds and water
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currents and polluted the coastline from the Shimane Prefecture through the Yamagata Prefecture. While much effort was made to remove the reached oil, many workers engaged in oil-removing complained of an eyeache, giddiness, a headache, etc. These symptoms were considered to be caused by volatile chemicals in the oil. Although the greater part of the oiled coastline was cleaned shortly after the oil pollution, there is concern that sands, rocks and sea water of the shore were still contaminated with chemicals included in the oil. Furthermore, some part has remained not to be treated. Extensive scientific studies were conducted to 1) evaluate the influence of volatile chemicals in the spilled oil on the health of oil-removing workers, 2) assess the impact of the spill on the ecosystem, 3) where and how long the contamination by the oil or chemicals persists in the environment. This paper reviews the activities and researches made after the Nakhodka oil spill accident.
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山本, 敦 ; 松永, 明信 ; 関口, 久義 ; 早川, 和一 ; 宮崎, 元一
概要:
Photometric ion chromatography is a novel method by using the photometer as a detector. A feature of this method is the use of light absorbing ion in the mobil phase, and the appearance of transparent sample ion in the effluent is
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detected by "trough"in the base line absorbance. We applied this technique by using a conventional HPLC system equipped with a commercially available ion exchange separation column to the determination of bromate in such foodstuffs as bread and kamaboko. Sample solution was prepared by aqueous extraction and mixed with acetone for removal of proteins. After evaporation of the organic solvent, the aqueous solution was dechlorinated by a DOWEX column (Ag-form), and then was subjected to chromatography. Samples of bread and kamaboko were spiked with 5.4 ppm and 8.4 ppm of bromate, respectively, and examined by the above method. The average recoveries were 88.3% in bread and 82.9% in kamaboko, and the coefficients of variation were 7.7% and 7.9%, respectively. The detection limit was 1 ppm. The above findings indicate that bromate can be detected by HPLC using conventional instrumentation, and the sensitivity of this system is comparable to conductimetric detection.
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早川, 和一 ; 山本, 敦 ; 宮崎, 元一
概要:
Ion chromatography (IC), which was introduced in 1975, has become widely used for the sensitive and simultaneous determination of ions. In the early stage, the IC system consisted of two ion-exchange columns (separator and suppressor,
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respectively) and a conductivity detector. Although this combination is still the most popular, new forms of separation and suppression have been developed. On the other hand, an indirect photometric detection using a UV detector has become popular in IC and other detectors commonly used in HPLC also have been used. Each of them has specific advantages for different types of analyses. Thus, IC is now defined as a form of liquid chromatography of ions. This article reviews new developments of the different forms of IC and their applications, especially to environmental samples, foods, biological materials and drugs, from reports published since 1990.
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吉田, 育世 ; 早川, 和一 ; 宮崎, 元一
概要:
Simultaneous determination of carboxylic acids and inorganic anions was investigated by photometric ion chromatography w
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ith phthalate solution as an eluent. The retention time and the peak area of carboxylic acids changed remarkably with eluent pH. The optimum conditions at present were as follows : analytical column, OYOBUNKO ASA-4000 (4.6 mm i.d.×25 cm) ; eluent, 5×10-4 M disodium phthalate ; flow rate, 2 ml/min ; column temperature, 40°C ; detection wavelength, 240 nm ; injection volume, 100 μl. The detection limits for several carboxylic acids as 3 times noise were 0.05-0.07 mg/l in sample solution. Their calibration curves showed straight lines by the peak area method. The present method has an advantage to determine simultaneously not only carboxylic acids but also inorganic anions. Under the condition described above, both carboxylic acids and inorganic anions in several liquid foods were easily determined by direct injection of the sample prepared with only dilution.
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松永, 明信 ; 山本, 敦 ; 水上, 英一 ; 早川, 和一 ; 宮崎, 元一
概要:
A high-performance liquid chromatographic method using post column reaction system was established for the determination
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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.
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宮崎, 元一 ; 早川, 和一 ; 飯田, 寿恵 ; 藤井, ちず子
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A simple method by using a column packed with Amberlyst-15 resin was established to remove metal ions which affect on PO
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V and TBA tests for lipid peroxidation. A methanol solution (2 ml) of lipid containing metal ions was applied to the column (0.5 cm×5 cm), and eluted with methanol (6 ml). Metal ions such as Cu2+, Fe3+ and Mn2+ were retained on the column, whereas linoleic acid, linolenic acid and methyl linolenate were completely recovered in the eluate (8 ml). By testing the peroxidized lipid with POV and TBA methods, the recoveries of the lipid mixture after the procedure were more than 85% (POV) and more than 99% (TBA). This pretreatment by using Amberlyst-15 column is available for the peroxidation tests of lipid.
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山本, 敦 ; 松永, 明信 ; 牧野, 正雄 ; 早川, 和一 ; 宮崎, 元一
概要:
A method for the simultaneous determination of organic acids was investigated by photometric ion chromatography by using
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two different eluents. A 4.6 mm i.d.×25 cm stainless column packed with MCI GEL SCA 01 (Mitsubishi Chemical Ind., Ltd.) was used as a separator column. Sample was injected into this column previously equilibrated with 1 mM citraconic acid at pH 6.8. After elution of monobasic organic acids, the eluent was exchanged to a stronger one, 1 mM m-sulfobenzoic acid at pH 6.8. Dibasic organic acids were eluted before the column reequilibration with the secondary eluent. On the other hand, tribasic organic acids such as citric acid were eluted with the secondary eluent. To prevent the base line disorder due to the eluent exchange, the determination at 254 nm was performed. Because this wave length is an isosbestic point of the two eluents. Sour-taste agents in soft drinks could be analysed directly after dilution of samples.
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早川, 和一 ; 宮崎, 元一
概要:
Ion chromatography (IC) with conductivity detection, which was introduced in 1975, has become widely used for the simultaneous determination of inorganic and organic ions. On the other hand, photometric ion chromatography (PIC) based on
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the difference of absorbances of sample and eluent (mobile phase) species has attracted much attention in the recent field of IC, since this technique has potential advantages over IC methods with conductivity detection. This technique which allows IC on a conventional single column HPLC system with an absorbance detector gives compatible sensitivity to conductivity detection. This paper deals mainly with indirect PIC methods performed by both ion exchange and reversedphase modes, where non-UV-absorbing ions are detected as positive and negative peaks by using UV-absorbing ions in the eluent (mobile phase). The features of PIC have been reasonably well known, but it is necessary to understand principles and conditions of PIC for the effective use of this technique. This paper reviews a number of significant reports which deal with the optimisations of separating column, eluent (mobile phase), detection wavelength, sensitivity and restrictions of PIC with its applications. It is also the purpose of this paper to discuss alternative methods and innovations of PIC.
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早川, 和一
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
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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.
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早川, 和一 ; 西尾, 和佳子 ; 宮崎, 元一
概要:
The lipoperoxidation in plasma was the most accelerated by the addition of 8-hydroxyquinoline (8HQ)-Fe (III) chelate among all 8HQ-metal chelate systems examined. The same tendency was also observed for 5-chloro-7-iodo-8HQ (C)-Fe
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(III) chelate system. The activity of 8HQ-Fe (III) system in lipoperoxidation was the highest at [8HQ]:[Fe (III)]=1: 1. In quinoline derivatives, the ligands which have 8-hydroxyl group and high solubility in lipid were necessary for lipoperoxidation in plasma by Fe (III) chelate systems. From above facts, both of the denaturation of nervous systems in SMON patients ad ministered with C and the antibiotic effects of 8HQ may be considered as the results of lipoperoxidation by C-Fe (III) chelate and 8HQ-Fe (III) chelate, respectively.
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木津, 良一 ; 東, 信一 ; 早川, 和一 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />血しょう及び尿中の制がん性白金錯体オキザラート(トランス-l-1,2-ジアミノシクロヘキサン)プラチニウム(II)(l-OHP)の分析法を研究した.種々検討した結果,分析条件は以下のように定めた.前処
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理;Dowex 1-X8,Dowex 50 W-X4及びSep-Pak C_<18>カートリッジを一連のカラムとして構成する.この前処理カラムに血しょう及び尿の1mlと引き続き水を流す.前処理カラム溶出液の最初の6ml部分は捨て,次の10ml部分を分取し,高速液体クロマトグラフィー(HPLC)の試料とした.HPLC条件;カラム:Finepak SIL C_<18>(4.6mm i.d.×25cm),カラム温度:50℃,溶離液:水-メタノール(95:5),流速:1ml/min,検出波長:210nm,試料注入量:100μlピーク高さによる検量線は,原点を通る良い直線性を示した.定量下限は,血しょう及び尿中l-OHP濃度0.5μM,再現性はR.S.D.3%程度であった.血しょう及び尿中のl-OHPを高感度で精度良く定量することができた. A method for determination of (trans-l-1, 2-diaminocyclohexane) oxalatoplatinum (II) (l-OHP), introduced by Kidani et al. as one of the promising antineoplastic platinum complexes, in plasma and urine by high performance liquid chromatography (HPLC) was investigated in order to contribute for metabolic study of l-OHP. The recommended pretreatment procedures and HPLC conditions are as follows. Pretreatment of plasma and urine ; pretreatment column is composed of Dowex 1-X8 (5mm i. d.×6cm), Dowex 50W-X4 (5 mm i. d.×3 cm) and Sep-Pak C_<18> cartridge. Blood samples are centrifuged at 1000 g for 3 min to obtain plasma. One ml of plasma or urine is immediately placed on the pretreatment column and is eluted with water at the flow rate of 1.2 ml/min. The initial 6 ml portion of effluent is discarded and subsequent 10 ml portion is collected. An aliquot (100 μl) of the effluent collected is subjected to HPLC. All of these pretreatment procedures are carried out at 5±2℃. HPLC conditions ; column : Finepak SIL C_<18> (4.6 mm i. d.×25cm), eluent : H_2O-MeOH (95 : 5), column temperature : 40℃, flow rate : 1 ml/min, detection wavelength : 210 nm, injection volume : 100 μl. Under the conditions described above, a linear relationship was obtained between peak height and l-OHP concentration in plasma and urine. Determination limit was 0.5 μM l-OHP in sample solutions. Recovery of l-OHP in pretreatment was 86±3% in plasma and 83±2% in urine. A sensitive and precise determination of l-OHP in plasma and urine will be possible by this method.
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早川, 和一 ; 蛯名, 令子 ; 松本, 美枝子 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />Determination of inorganic anions and cations in some vegetable juices was examined by ultraviolet p
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hotometric ion chromatography with a conventional HPLC system equipped with a UV monitor and a separating column packed with popular ion exchangers. Inorganic anions such as Cl^-, NO_3^-, and SO_4^<2-> in sample solution were completely separated on a Zipax SAX packed column (50 cm × 2.1 mm I. D.) with 5 × 10^<-3> M disodium phthalate as an eluent and detected at 240 nm. Inorganic cations such as Na^+, NH_4^+, K^+, Mg^<2+>, and Ca^<3+> in sample solution were completely separated on a Zipax SCX packed column (25 cm × 4.6 mm I. D.) with 2.5 × 10^<-3> M copper sulfate as an eluent and detected at 220 nm. Under the conditions described above, the three anions in juices of Chinese cabbage, tomato, and radish, and the five cations in Sep-pak C_<18> treated juice of Chinese cabbage were determined.
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| 27.
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村田, 勝夫 ; 山下, 伸典 ; 小川, 伸明 ; 早川, 和一 ; 谷口, 博士
概要:
金沢大学医薬保健研究域薬学系<br />銅板の日本海型腐食を調べるため, 秋田県, 石川県, 鳥取県の3県に数ヶ所の観測点を設け, 定期的に試料を回収して, その表面を高感度反射・フーリエ変換赤外分光法を用いて分析した.その結果, 腐食生成
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物に関して新な化学種の生成は見られなかったが, 表面の酸化物やスルファト錯体の生成の面で, 冬季に著しい腐食反応の進行が見られた.この点は, 瀬戸内海側や太平洋側での観測結果と非常に異なる特徴を示している.又臨海部の試料に特徴的な赤外スペクトルにおけるベースラインの高波数領域への斜傾化は, エメリーペーパーによる試料表面の研磨による検討から, 表面の物理的荒れ現象であることが判明した. Copper plates were exposed to the ambient atmosphere in locations at different distances from the Sea of Japan coastline in order to investigate matal corrosion characteristic of weathering in winter. The samples from along the Sea of Japan coastline at Akita, Kanazawa, and Tottori districts were compared with those of Naruto district. The samples were analyzed by FT-IR reflection absorption spectroscopy (RAS). The formation of sulfato complexes and hydroxy species as well as oxides of Cu_2O and CuO was observed on the samples in all regions, but the formation rate of their species was different. The formation rate of the species from samples along the Sea of Japan coastline rapidly proceeds while that of the samples in Naruto district proceeds slowly in the winter season. Polishing the surface of the copper plate with emery paper revealed that an oblique baseline observed in the IR-RAS spectrum of the corroded samples is attributable to roughness on the surface of the copper plates which is mainly caused by weathering.
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| 28.
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綿谷, 敏彦 ; 早川, 和一 ; 能村, 京子 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />The differential chromatogram method was useful to reduce large changes in background response in si
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ngle column ion chromatography using stepwise elution. Cations (Na^+, K^+, Mg^<2+> and Ca^<2+>) were separated on cation exchange column by stepwise elution using both 0.01 mM and 3.0 mM copper sulfate eluents and detected at 230 nm by indirect photometry. Anions (lactate, acetate, propionate, formate, citrate, Cl^-, NO_2^-, Br^-, NO_3^-, SO_4^<2->, S_2O_3^<2-> and I^-) were separated on an anion exchange column using both 0.3 mM and 1.5 mM disodium phthalate eluents and detected at 270 nm. This method was also successfully applied to conductometric detection.
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| 29.
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石川, 雅章 ; 山本, 政利 ; 増井, 俊夫 ; 早川, 和一 ; 宮崎, 元一 ; 中澤, 裕之 ; 藤田, 昌彦
概要:
金沢大学医薬保健研究域薬学系<br />Determination of inorganic ions in aqueous infusions was studied by photometric ion chromatography (
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PIC) using a conventional HPLC system equipped with a UV monitor. Inorganic cations (Na^+, K^+, Mg^<2+> and Ca^<2+>) could be separated on a strong cation exchange column, Oyobunko ASC-4000 column (4.6 mm i. d.×250 mm), with 1×10^<-4> M CuSO_4 for Na^+, K^+ and 2×10^<-3> M CuSO_4 for Mg^<2+>, Ca^<2+> as eluents, and detected at 220 nm. Inorganic anions (Cl^-, PO_4^<3-> and SO_4^<2->) could be separated on a strong anion exchange column, Oyobunko ASA-4000 column (4.6 mm i. d.×250 mm), with 1×10^<-3> M disodium phthal- ate (pH 10) as an eluent, and detected at 260 nm. A sample solution was simply diluted with distilled water, and could be analyzed by PIC. Relative standard deviations (n=5) for above ions in a commercial infusion were below 2.0%.
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| 30.
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村橋, 毅 ; 早川, 和一 ; 岩本, 侑子 ; 宮崎, 元一
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
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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.
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| 31.
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木津, 良一 ; 加藤, 詳子 ; 薄井, 修 ; 早川, 和一
概要:
金沢大学医薬保健研究域薬学系<br />エストロゲン作用の新しいin vitroアッセイ法として, ヒト乳がん由来MCF-7細胞におけるプロゲステロン受容体(PgR)の発現量を指標とする方法を提案し, 現在最もはん用されてぃるE-Scree
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nアッセイ法と比較するとともに, C重油のエストロゲン作用を検討した. 試料としては, 重油のエタノール抽出物を用いた. PgRの発現量をウエスタンブロット法で測定したところ, 17β-エストラジオール(E_2)処理によりPgRの発現量が高まり, 更にE_2アンタゴニストであるタモキシフェンの処理を加えるとPgRの発現量は減少した. E-Screenアッセイにおいても, E_2及びタモキシフェン処理に対して類似の応答を示し, PgR発現量がエストロゲン作用の良い指標であることが明らかになった. 次に, 重油抽出物のエストロゲン作用について検討した. E_2非存在下では重油抽出物の処理でわずかながらPgRの発現量が高まったが, E_2存在下ではPgRの発現量は減少した. 以上の結果から, 重油中には弱いエストロゲン作用を示し, E_2アンタゴニストとして作用する化合物が含まれることが明らかとなった. また, 重油抽出物の処理では死細胞数の増加が観察された. 重油や環境試料のように細胞死を引き起こす成分を含む可能性がある試料については, 本研究のPgRの発現量を指標とする方法が適していると考えられた. The authors have proposed a new in vitro assay method for estrogenicity. The cellular progesterone receptor (PgR) level in the human breast cancer cell line MCF-7 was measured because PgR has been known to be upregulated by 17β-estradiol (E_2). The cellular PgR level was measured by a western blotting technique. While an E_2 treatment increased the PgR level, tamoxyfen, a typical E_2 antagonist decreased the PgR level elevated by the E_2 treatment. These results revealed that the cellular PgR level is a good indication to evaluate the estrogenicity. Next, the estrogenic activities of Nakhodka heavy oil and a commercial C-heavy oil were examined. Heavy oil crude extracts prepared with ethanol were subjected to the assay. While the extracts increased the PgR level under the E_2-free condition, the extracts decreased the PgR level elevated by the E_2 treatment. These results indicate that the heavy oil contains compounds which show weak estrogenic activity and act as E_2 antagonists. Dead cells were observed after the oil extract treatment, and their number increased with an increase of oil extract concentration in the cell-culture medium. Environmental samples such as oil-extract, river water, and air particulate extract comprise a wide variety of compounds, and are thought to have a cell-killing effect. A cellular PgR expression method is considered to be more appropriate for assessing the estrogenic activities of environmental samples, compared with the existing assay methods, such as the cell-proliferation method (E-Screen assay) and the reporter-gene methods.
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| 32.
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中村, 誠治 ; 今泉, 範子 ; 早川, 和一 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />ノンサプレッサー型イオンクロマトグラフィー(IC)としてはん用される電気伝導度検出ICと間接吸光度検出ICの感度特性を検出原理式に基づき,強酸性物質と弱酸性物質について比較した.両法に用いることができ
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る溶離液種として安息香酸及びフタル酸を用いると,硝酸イオンなどの強酸性物質の検出では,低pH溶離液の電気伝導度検出のほうが感度が高く,弱酸性物質の検出では,高pH溶離液の間接吸光度検出のほうが高かった.共通溶離液としてはん用される低pHのフタル酸溶離液を用いたときの両者による強酸性物質の分析値の相関は良かった.又,溶離液として,1,5-ナフタレンジスルホン酸やベンゼンジスルホン酸を用いると,間接吸光度検出による感度を向上させることができ,強酸性物質の検出でも低pHフタル酸溶離液を用いたときの感度を上回った. The detection sensitivities of anionic compounds by conductivity detection (CD) and indirect photometric detection (IPD) were compared in non-suppressed ion chromatography. The reciprocal of peak area to noise ratio was used to compare the two detection methods for such common eluents as benzoate and phthalate at pH 4.3 and pH 6.7. The sensitivities of strong acid compounds were highest by CD at pH 4.3, while those of weak acid compounds were highest by IPD at pH 6.7. These results were consistent with theoretical equations for the two detection methods. The sensitivities of strong acid compounds by IPD exceeded those by CD with the phthalate eluent at pH 4.3, using eluent species such as 1, 5-naphthalenedisulfonate. Correlations between the two methods were excellent in the determination of inorganic anions in soluble fractions of monthly collected deposits
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| 33.
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早川, 和一 ; 平木, 博美 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />入手が容易なイオン交換カラムを備えた普及型HPLC装置で可能な,無機陰イオンの微量分析条件を検討した.無機陰イオン(炭酸イオン,塩化物イオン,亜硝酸イオン,リン酸イオン,臭化物イオン,硝酸イオン,硫酸
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イオン,ヨウ化物イオン)は,フタル酸二ナトリウム溶液を溶離液として,陰イオン交換カラムで分離溶出された後,ベースラインの谷として紫外検出される.炭酸イオン,塩化物イオン,リン酸イオン,臭化物イオン,硝酸イオン,硫酸イオンの同時分析の最適条件は,カラム:Zipax SAX (2.1 mm i.d.×50cm):溶離液:5×10^<-4> Mフクル酸二ナトリウム;流速:1 ml/min; 温度:室温;検出波長:240 nm;注入量:100μlであった.この条件で,検出下限はppbレベルであり,ピーク高さ法と面積法のいずれでも検量線は直線となった.本法を用いると,環境試料中の主要無機陰イオンが短時間に一斉分析でき,しかも本法の分析値は,他法の結果ともよく一致した. A photometric determination method of microamounts of inorganic anions has been developed by conventional high performance liquid chromatography using a popular ion exchange column. Inorganic anions (HCO_3^-, Cl^-, NO_2^-, H_2PO_4^-, Br^-, NO_3^-, SO_4^<2->, and I^-) were separated on an anoin exchange column by using disodium phthalate solution as an eluent, and detected as troughs in the base line absorbance by a UV monitor. The optimum conditions for the determination of HCO_3^-, C1^-, H_2PO_4^-, Br^-, NO_3^-, and SO_4^<2-> were as follows : column, Zipax SAX (2.1 mm i.d. ×50cm) ; eluent, 5×10^<-4>M disodium phthalate ; flow rate, 1 ml/min ; column temperature, ambient ; detection wavelength, 240 nm. Under the conditions described above, detection limits of these anions were at levels as low as ppb. The calibration curves gave straight lines by either peak height or peak area method. Main inorganic anions contained in environmental samples could be simultaneously determined by the proposed method, and their analytical results were close to those obtained by other methods.
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| 34.
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早川, 和一 ; 山本, 敦
概要:
金沢大学医薬保健研究域薬学系<br />これまで, 液体クロマトグラフィーにおける吸光度検出器は専ら光吸収を有する化合物を検出する装置であり, その原理と検出器は既に完成されたものとの印象が強かった.本総説は, 上述の概念を大きく変革しつつ
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ある吸光度検出法の新展開として, 光吸収のない対象物質を検出できる間接吸光度検出法と, 更にその考え方を光学活性物質の検出に向けた偏光吸光度検出法に焦点を合わせ, 著者らの研究成果も含めて紹介する. New photometric detection methods developed for use in liquid chromatography have been reviewed. Differential photometric detection using UV-visible absorbing modifiers enabled us to examine the retention and detection mechanism of not only analytes but also mobile phases. Indirect photometric detection ion chromatography based on this theory separately and sensitively determines ionic compounds using a conventional high-performance liquid chromatographic system with a UV-visible absorbance detector. This method is useful for many kinds of samples such as environmental water, foods and biological materials. Polarized photometric detection mathods with two polarizers on either side of a UV-visible absorbance detector flow cell have been developed. The monitor determines optically active compounds as the change in absorbance. This method was effectively applied for determining sugars and organic acids
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| 35.
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早川, 和一 ; 平木, 博美 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />A novel method for the determination of micro amounts of inorganic ions has been developed. The sepa
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ration of alkaline metal ions (Li^+, Na^+, and K^+) was accomplished on a Zipax SCX packed column (4.6 mm × 12 cm) with 2.5×10^<-4> M copper sulfate as an eluent, and the separation of halogen ions (F^-, Cl^-, and Br^-) was accomplished on a Zipax SAX packed column (4.6 mm × 15cm) with 1.0 × 10^<-3> M sodium benzoate as an eluent. The eluted ions were detected as troughs in base line absorbance of eluent ion at 220 nm or 240 nm. Under the conditions described above, the six ions were easily separated and determined at the levels as low as ppb by using either a peak height method or a peak area method which gave straight calibration curves. Other inorganic ions can be also determined by changing composition and concentration of the eluent. Moreover, this analytical method is economical and simple, since it can be performed with a conventional HPLC system equipped with a single separation column packed with inexpensive and easily available ion exchanger and a photometric detector.
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| 36.
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早川, 和一 ; 西島, 美知子 ; 宮崎, 元一
概要:
金沢大学医薬保健研究域薬学系<br />A novel method for the separation of halogenated anion complexes of platinum metals by reversed-phas
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e ion-pair partition chromatography has been developed. The separation of RhBr_5^<2->, PdBr_4^<2->,and PtBr_6^<2-> was accomplished on a Hitachi #3050 packed column (3mm×30cm), where 30 % (v/v) acetonitrile-0.02 M phosphate buffer (pH 7) mixture containing 0.1 M tetrabutylammonium bromide and 0.025 M sodium bromide was used as a mobile phase. These anion complexes can be determined at 310nm, and as low as 5×10^<-11> mol of PtBr_6^<-2> can be determined with the peak height method which gave a straight calibration curve. Detecting wavelengths and retention times of the complexes can be altered if the complexes are formed with other halogen ions. This analytical method for micro amounts of platinum metals can remove the mutual metal interferences.
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| 37.
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早川, 和一 ; Hayakawa, Kazuichi
概要:
1.ニトロアレーン分析法の改良:既報の化学発光検出HPLCによるトロアレーン分析システムにニトロアレーン分離用ODSカラム,亜鉛還元カラム,高圧流路切り替えバルブ等を導入することにより,極微量ニトロアレーンの分析システムを完成した.これによ
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り,数mg以下の大気粉じん中の2-ニトロフルオランテン(2-NF),2-ニトロピレン(2-NP),4-NP,6-ニトロクリセン(6-NC)等を定量可能とした.2.ディーゼル粉塵抽出物の直接変異原性におけるニトロアレーンの寄与:ディーゼル粉塵のbenzen-ethanol(3:1)抽出物をシリカゲルカラムクロマトグラフィー(n-hexane,dichloromethane,methanolの混合溶媒)で5分画した.Ames試験による直接変異原性(S.typhimuriumYG1024株)は高極性溶媒(dichloromethane-methanol及びmethanol)の2分画に集中し,ニトロアレーンはこのうちの前者に集中した.直接変異原性におけるニトロアレーン(8種)の寄与率はこの分画で50%余り,全分画合計の約1/3に達し,大きいことが明らかになった.3.札幌,東京,金沢の大気環境比較:金沢市,東京都,札幌市の大気中DNP及び1-NP濃度は札幌≧東京>金沢の純に低くなったが,都心は都市による差は小さかった.3都市の中では,札幌が1,3-,1,6-,1,8-ジニトロピレン(DNP)濃度に対する1-NP濃度の比が最も大きく,その理由の一つとして,ディーゼル車の保有台数の割合が高いことが考えられた.濃度推移は日内変動(昼高夜低)及び季節変動(夏低冬高)を呈したが,都市により程度に差があった.4.大気中のニトロアレーンの分解と二次生成:金沢市内の都心と郊外の大気中ニトロアレーンの比較により,DNP及び1-NPは大気輸送中に分解し,その主要因が太陽による光分解であることがわかった.また、2-NFと2-NPはディーゼル粉塵には検出されず郊外ほど存在比が大きくなることより,大気中で二次生成することが推定された.<br />(1) We introduced another separation column (ODS), a zinc reducer column and a switching valve into the nitroarene analyzer, a HPLC equipped with a chemiluminescence detector, to determine trace levels of nitroarenes.(2) Benzene-ethanol extracts from diesel exhaust particulates were separated into 5 fractions on a silica-gel column with mixtures of n-hexane, dichloromethane and methanol. The strong direct-acting mutagenicities were observed in the dichloromethane-methanol and methanol fractions in the Ames test using the S.typhimurium YG1024 strain and nitroarenes were mainly in the former fraction of the two. The mutagenic contribution of nitroarenes were 1/3 of the all fractions. The large contribution of nitroarenes to the mutagenicity of urban air suggests that the monitoring of nitroarenes is very important for assessing the risk of air pollutants.(3) Concentrations of 1,3-, 1,6- and 1,8-dinitropyrenes (DNPs) and 1-nitropyrene (NP) in urban air were in the following decreasing order, Sapporo>Tokyo>Kanazawa. However, the concentrations in downtown areas of the three cities were at similar levels. The relative concentration of DNPs to that of 1-NP was the highest in Sapporo. As a reason, the large ration of diesel-engine vehicles was considered. Their concentrations showed diurnal and seasonal variations.(4) The relative concentrations of DNPs and 1-NP to polycyclic aromatic hydrocarbons were lower in the suburban areas than in the downtown areas, suggesting that DNPs and 1-NP degradated in the presence of sun light during the transportation. On the other hand, the fact that both 2-nitrofluoranthene (NF) and 2-NP were not detected in diesel exhaust particulates but detected in airborne particulates suggested that these two compounds were formed in air.<br />研究課題/領域番号:08672472, 研究期間(年度):1996–1997<br />出典：「未規制大気汚染物質ニトロアレーンの動態解析とその軽減に関する基礎研究」研究成果報告書 課題番号08672472(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
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| 38.
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早川, 和一 ; Hayakawa, Kazuichi
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)
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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
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| 39.
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論文
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早川, 和一 ; Hayakawa, Kazuichi
概要:
(1)金沢市市街地の大気中1,3-,1,6-,1,8-ジニトロピレン(DNP)及び1-ニトロピレン(1-NP)の平均濃度は,それぞれfmol m^<-3>,サブpmol m^<-3>〜pmol m^<-3>レベルであった.これらの化合物濃度
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は,日中に高く夜間から早朝に低い日内変動を示し,交通量と高い相関が認められたことより,主要発生源は自動車と推定された.また,これらの化合物濃度は春から夏に低く,秋から冬に高い季節変動を示し,その要因の一つとして,前者には太陽光による光分解が,後者には逆転層による大気の安定が考えられた. (2)ガソリン車とディーゼル車の排ガス中DNP,1-NP濃度及び粉じん量を比較すると,DNP濃度は大差ないが,後者は前者に比べて1-NP濃度が遙かに高く,粉じん量も多い.これらに基づいて金沢市市街地の大気中DNP,1-NPについて発生源としてのディーゼル車の寄与率を求めると,それぞれ約90%,99%以上と試算された. (3)金沢市,東京都,札幌市の大気中DNP及び1-NP濃度には,都市の特徴によって多少の違いがあるものの,類似した日内及び季節変動が認められた.3都市の中では,札幌市がDNP濃度に対する1-NP濃度の比が最も大きく,その理由として,ガソリン車に対するディーゼル車の保有台数の割合が高いことが考えられた. (4)大気中1,3-,1,6-,1,8-DNP及び1-NP濃度推移と,Ames試験による大気直接変異原活性推移との相関は高く,上記化合物の大気直接変異原活性における寄与率は,YG1024株では約30%,TA98株では約10%と試算された.粒径別では,肺胞に沈積する割合の高い1.1μm以下の最微細粉じんに,化合物と変異原活性のいずれも最も多く分布していることが明らかとなった.大気変異原性に寄与するDNP,1-NP以外の化合物は,シリカゲルカラムクロマトグラフィーにより,DNPよりも低極性であると推定された.<br />(1) Each mean concentration of 1,3-dinitropyrene (1,3-DNP), 1,6-DNP,1,8-DNP and 1-nitropyrene (1-NP) in air in downtown Kanazawa were in the levels of fmol m^<-3> and sub pmol m^<33>-pmol m^<-3>, respectively. The concentrations were high in the daytime and low in the midnight and early in the morning. This diurnal variation gave a good correlation to the traffic volume, suggesting automobiles were the main contributors. The concentrations were high in spring and summer and low in autumn and winter. As reasons for this, degradation by sunlight in the former seasons and low atmospheric mixing dephts in the latter seasons were considered.(2) Concentrations of 1,3-, 1,6-and 1,8-DNPs and 1-NP in air in winter and summer in downtown Kanazawa, Sapporo and Tokyo were determined. Although the mean concentrations in Kanazawa were lower than those in Tokyo and Sapporo, there were similar tendencies as described above. The 1-NP to DNPs ratio in Sapporo was the largest in the three cities, suggest ing the largest diesel-engine vehicles to gasoline-engine vehicles ratio.(3) Concentrations of 1,3-, 1,6-and 1,8-DNPs in diesel Particulate were at the same levels as those in gasoline particulate. However, the concentration of 1-NP in diesel particulate was much higher than that in gasoline particulate. Considering the amount of particulates emitted from diesel-engine much larger than that of gasoline-engine, the contribution of diesel-engine vehicles to the amount of the above compounds in urban air was much larger than that of gasoline-engine vehicles.(4) In both diurnal and seasonal variation studies, good correlation coefficients were observed between the four concentrations and direct-acting mutagenic activities by the Ames test using three stains, TA98, YG1021 and YG1024. In the three, the YG1024 gave the largest coefficient. The contributions of the four compounds to the activities of air in YG1024 and TA98 strains were about 30% and 10%, respectively. The silica gel column chromatography suggested that the other contributors were less polar. When particulates were separately collected into five fractions of different particulate sizes, both the compounds and the activity were mainly contained in the finest particulate fraction (less than 1.1um) which was most adsorbed in alveoli of the lung.<br />研究課題/領域番号:06672138, 研究期間(年度):1994–1995<br />出典：「ニトロアレーンの環境動態解析とその軽減に関する基礎研究」研究成果報告書 課題番号06672138(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
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論文
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早川, 和一 ; Hayakawa, Kazuichi
概要:
1.イオンクロマトグラフィ-(IC)の保持・溶出機構解析:溶離剤成分と試料成分の挙動解析から選択的ピ-ク増感・抑制の理論を提案し、微量リン酸の分析に応用した。Hooverモデルに基づく関係式に新しく溶離剤間分離係数を導入し、二塩基酸溶離液系
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でも試料成分と溶離静成分の挙動が理論的に推定できるようにした。2.自動前処理IC:カラムスイッチング法の導入により、陰イオン分析を妨害するアルカリ土類金属のオンライン除去ICを開発した。このシステムは、生活雑排水中のリン酸分析を妨害する成分のオンライン除去にも有効であった。また、電気伝導度検出ICで報告されている自動濃縮分析システムを吸光度検出ICについて考案した。このシステムは、極地氷床コアや雨水等の希薄環境試料の分析に有効であった。3.吸光度検出IC用機能性溶離剤:配位子交換吸光度検出IC理論に基づく光学異性有機酸の分析法を開発した。本法で前処理なしに清涼飲水中の添加リンゴ酸の分析ができた。4.炭酸のIC:大気中の二酸化炭素の妨害を除去して微量炭酸が分析できる窒素通気ーイオン排除クロマトグラフィ-を開発した。これにより雨水中の炭酸が数種の低級有機酸と同時分析できた。5.偏光吸光度検出法:吸光度検出セルの前後に二枚の偏光子を設置すると、吸光度変化量はセル内に存在する光学活性物質の濃度に比例するという偏光吸光度検出理論を提案した。本法は紫外・可視吸収がなく光学活性がある糖などの分析に適用でき、その検出感度も優れていた。6.化学発光検出HPLCによるニトロピレン類の超高感度分析法:オンライン電気化学還元ー化学発光検出HPLC及びオフライン化学還元ー化学発光検出HPLCによるニトロピレン類の超高感度分析法を開発した。これらの方法で、ニトロピレン類の主要排出源の一つと言われているディ-ゼル及びガソリン自動車排ガス中のジニトロピレンが分析できた。<br />(1) Theoretical studies on the retention and peak formation mechanism in ion chromatography (IC) : Following on from our previous work, a new theory "selective peak enhancement and suppression of conductivity detection IC" was evaluated. This theory was effectively used in the determination of trace level orthophosphate in sewage samples. Ion exchange chromatographic behavior of polyvalent eluent systems was evaluated theoretically by introducing a new parameter "the intereluent separation factor" in equations for Hoover's model.(2) Functional eluents for photometric detection IC : Both[Cu(en)_2SO_4 and[Cu(trien)]SO_4 were effective eluents for the sensitive determination of cations. Using a Na_2[Cu(edta)]- Na_2H_2 edta eluent, not only anions but also metal ions were deterifined as metal-edta anion chelates by photometric detection IC. These methods were effectively used in the determination of cations and anions in environmental water samples. Malic acid enantiomers were separately d etermined by photometric detection IC using a copper - tartaric acid complex eluent, based on a ligand-exchange formation mechanism. Malic acid, an apple juice additive, was determined by this method.(3) Determination of carbonate-carbon : Interfering atmospheric carbon dioxide dissolved in eluents was removed effectively by nitrogen purging. Using this equipment, trace level carbonate carbon as low as 10^<-6> M could be determined by photomeric detection IC as well as ion exclusion chromatography (conductivity detection). Carbonate-carbon in rain water was determined by this method.(4) Polarized photometric detection : When two polarizers were set on both sides of the flow sell of an absorbance detector, the intensity of natural light transmitted through the polarizers and the flow cell was changed according to the optically active compounds if passed through. The change in absorbance was in proportion to the concentration of the compound. Nonchromophoric optically active compounds such as sugars were sensitively determined using photometric detection HPLC without any derivatization.(5) Automatic pretreatment/HPLC system : The combination of column-switching system and a heart-cutting technique effectively removed interfering compounds in IC. This system was used to determine anions in river and rain water samples by photometric detection IC and orthophosphate in sewage samples by conductivity detection IC.(6) Determination of nitopyrenes by HPLC with chemiluminescence detection : A method of determining nitro-, nitroso- and aminopyrenes has been developed using HPLC with chemiluminescence detection after on-line electrochemical reduction. Determination method of 1, 3-, 1, 6-, 1, 8-dinitropyrenes and 1-nitropyrene has also been developed using HPLC with chemiluminescence detection after off-line chemical reduction. Utilizing these methods, dinitropyrenes and nitropyrene were determined in diesel- and gasoline-engine exhaust particulates.<br />研究課題/領域番号:02670975, 研究期間(年度):1990–1991<br />出典：「新しい吸光度検出方式高速液体クロマトグラフィーの応用研究: 環境汚染分析法の開発」研究成果報告書 課題番号02670975(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
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