Spectrophotometric determination of copper by the ion exchange extraction with aluminum cupferrate and the ligand exchange with sodium diethyldithiocarbamate
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Abstract:
アルミニウム-クペレート{Al(Cup)3}のクロロホルム溶液を用いて溶媒抽出を行うと,アルミニウムより抽出定数の大きい銅(II)が選択的に抽出される.有機相をジエチルジチオカルバミン酸ナトリウム(Na-DDTC)の水溶液と振り混ぜると,銅(II)-クペレートは配位子交換により,銅(II)-DDTCキレートに変わることを見いだした.この反応を利用して,微量の銅(II)を選択的に定量した.抽出剤に用いたAl(Cup)3は無色で,Na-DDTCと配位子交換を起こさないので,黄かっ色の銅(II)-DDTCキレートを436nmで吸光光度定量できる.この方法を,アルミ合金及びニッケル,コバルト,亜鉛,カドミウム,銀塩などの試薬中の微量の銅の定量に適用した.Keywords:
Sodium diethyldithiocarbamate
Sodium diethyldithiocarbamate
Penicillamine
Tissue distribution
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OBJECTIVE:To establish a HPLC method for the determination of diethyldithiocarbamate in the sodium diethyldithiocarbamate(DDC) for injection.METHODS:The determination was performed on Phenomenex C8,the mobile phase consisted of 0.1% phosphate buffer(pH=6.3)(which contained 0.0 125mol/L tetrabutyl ammonium chloride)-methanol(65∶35) with a flow rate of 1.0ml/min,the detection wavelength was 257nm and the sample size was 20μl. RESULTS: The linear detection concentration range of DDC was 50～800μg/ml(r=0.9 998),the average recovery was 99.53%(RSD= 0.98%).CONCLUSIONS:The method was simple,rapid and reliable,and suitable for the quality control of DDC for injection.
Sodium diethyldithiocarbamate
Linear range
Recovery rate
Ammonium chloride
Phosphate buffered saline
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A precise and sensitive analytical method was developed for the determination of heavy metals in food.Diisobutyl ketone (DIBK), which is far less soluble in water compared to methyl isobutyl ketone or n-butyl acetate, was used with sodium diethyldithiocarbamate (DDTC) in the solvent extraction separation-flame atomic absorption spectrometry system. Cadmium, nickel, cobalt, lead and copper in alkaline solution (pH 13) could be extracted with DDTC into DIBK without interference from iron and manganese.The proposed method was satisfactorily applied to the analysis of the environmental reference materials (pepperbush, chlorella and mussel) and some foods. The recoveries of these metals from foods were 95.3-102.6% and the relative standard deviations were 0.2-3.2%. Practical detection limits were generally 0.001μg/g for cadmium, 0.002μg/g for copper and 0.01μg/g for nickel, cobalt and lead.
Sodium diethyldithiocarbamate
Methyl isobutyl ketone
Trace Amounts
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In the atomic absorption spectroscopic determination of cadmium, ammonium pyrrolidyldithiocarbamate (APDC) was used as the chelating reagent but it was found that sodium diethyldithiocarbamate (DDTC) was better than APDC. Cadmium pyrrolidyldithiocarbamate was slightly soluble in most organic solvents and fairly soluble only in methyl isobutyl ketone, but cadmium diethyldithiocarbamate was easily soluble in most organic solvents. Therefore, extraction efficiency of cadmium complex from the aqueous solution with methyl isobutyl ketone was very good in the case of cadmium diethyldithiocarbamate. This experimental fact resulted in the simplified procedure and high recovery ratio.
Sodium diethyldithiocarbamate
Methyl isobutyl ketone
Cadmium acetate
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Sodium diethyldithiocarbamate
Sodium salt
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Sodium diethyldithiocarbamate and disulfiram have been proposed as effective nickel chelators. This paper examines the value of these compounds in the treatment of acute nickel carbonyl poisoning by reviewing published experimental and clinical data.In 2 studies, parenteral administration of diethyldithiocarbamate 50-100 mg/kg to rats immediately following nickel carbonyl exposure ensured the survival of all animals: Mortality fell from 73% to 8% when diethyldithiocarbamate was administered at 10 minutes in a third study. In the same study, there was no protection when diethyldithiocarbamate was administered at 6 hours, and the mortality was greater, though not significantly different, when diethyldithiocarbamate was administered at 24 hours. In another study in mice, total protection was afforded by diethyldithiocarbamate given at 8 hours but this protection was limited when diethyldithiocarbamate was administered at 24 hours, with diethyldithiocarbamate 100 mg/kg apparently being less protective than diethyldithiocarbamate 50 mg/kg. In 3 studies, oral diethyldithiocarbamate administration was less effective than parenteral administration. There are no adequately controlled clinical studies of the use of diethyldithiocarbamate in acute nickel carbonyl poisoning despite claims that this therapy has been effective in the treatment of several hundred such patients. Disulfiram, a metabolite of diethyldithiocarbamate, offered complete protection against nickel carbonyl-induced toxicity when administered in a dose of 1000 mg/kg to rats immediately following nickel carbonyl exposure. In contrast, disulfiram 500 mg/kg offered no protection and disulfiram 1500 mg/kg appeared to enhance mortality, possibly by increasing brain nickel accumulation.Animal studies demonstrate that diethyldithiocarbamate is an effective antidote in acute nickel carbonyl poisoning when it is administered parenterally soon after exposure. However, as no adequately controlled clinical studies have been performed, further clinical data are required before diethyldithiocarbamate can be recommended routinely in acute nickel carbonyl poisoning. If diethyldithiocarbamate is to be employed, it should be administered parenterally soon after exposure as delay in administration may increase nickel carbonyl toxicity. There are currently insufficient data to recommend disulfiram as an alternative to diethyldithiocarbamate even when diethyldithiocarbamate is not available.
Sodium diethyldithiocarbamate
Disulfiram
Antidote
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Whole-body autoradiography and liquid scintillation counting were used to study the effect of sodium diethyldithiocarbamate on the tissue disposition of 63nickel in mice exposed to 63nickel carbonyl by inhalation or intraperitoneally. The sodium diethyldithiocarbamate markedly affected the disposition of the 63nickel in several tissues. Diethyldithiocarbamate forms lipophilic chelates with many metals, including nickel, and the mobilization of the 63nickel is probably due to a redistribution in the tissues of the complex formed. In the lung--the principal target tissue for nickel carbonyl--a decrease was observed, and this may be the reason for the beneficial effect of sodium diethyldithiocarbamate in nickel carbonyl intoxications. In mice which were exposed to 63nickel carbonyl by inhalation, the level of 63nickel in the brain was very high and the sodium diethyldithiocarbamate reduced this labelling. Intraperitoneal injections of 63nickel carbonyl resulted in a low labelling of the brain, and in this instance an increased brain radioactivity was induced by the sodium diethyldithiocarbamate. This observation can probably be explained by an affinity of the lipophilic nickel-diethyldithiocarbamate complex for the lipid-rich brain tissue.
Sodium diethyldithiocarbamate
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Sodium diethyldithiocarbamate, D-penicillamine, and triethylene-tetramine were administered to rats by im injection in dosages equivalent to 0.6 times their respective LD50 values in order to compare their relative effectiveness in prevention of death caused by exposure for 15 min to inhalation of nickel carbonyl (1.4 or 4.2 mg Ni (CO)4/liter of air). When the three drugs were administered to groups of rats at 10 min before or after the exposure to nickel carbonyl, sodium diethyldithiocarbamate was the most effective antidote. In contrast, then the drugs were administered at 6 hr after exposure to nickel carbonyl, D-penicillamine was the most effective antidote. Based upon the combined results of 4 sets of experiments, sodium diethyldithiocarbamate and D-penicillamine were significantly more effective than triethylenetetramine. The authors recommend that sodium diethyldithio-carbamate should remain the chelating agent of choice for therapy of nickel carbonyl poisoning. If sodium diethyldithiocarbamate is not available or if its use is contraindicated, D-penicillamine might be considered as an alternative chelating agent.
Sodium diethyldithiocarbamate
Antidote
Triethylenetetramine
Penicillamine
Dimercaprol
Tetramine
Dose
Sodium citrate
Dithiocarbamate
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Aluminium-27 nuclear magnetic resonance studies of sulphato-complexes of the hexa-aquo aluminium ion
A sulphato-aluminium complex and a small amount of dimeric aluminium cation have been detected in aqueous aluminium sulphate solutions by means of 27Al n.m.r. spectroscopy. The sulphato-complex is probably formed from the SO42– rather than the HSO4– ion. The results emphasise the complexity of aluminium sulphate solutions and may throw light upon the old controversy over the exact proportion of water present in aluminium sulphate crystals.
HEXA
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The method described for determining copper is based on a complexation reaction effected in acetic acid solution. The acetic acid not only effects complexation but also dissolves the complex and no intermediate extraction is therefore necessary. The sensitivity is higher than that for other methods based on diethyldithiocarbamate. Various metal ions interfere in the determination of copper using diethyldithiocarbamate and the elimination of these interferences is discussed.The application of the method to the determination of trace amounts of copper in various biological materials, particularly foodstuffs, is discussed.
Sodium diethyldithiocarbamate
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