Simultaneous determination of cationic surfactants and nonionic surfactants by ion-association titration.

A simultaneous determination of cationic and nonionic surfactants has been developed using ion-association titration. Tetrabromophenolphthalein ethyl ester (TBPE) was used as an indicator. Benzalkonium reacted with TBPE to form a blue ion-associate in the organic phase. When tetrakis(4-fluorophenyl)borate was added dropwise to the solution, the color of the organic phase turned to yellow at the equivalence point. In addition, when a large amount of potassium ion was added to a solution including Triton X-100, Triton X-100 could be determined by the same technique as described above because of formation of the K+-Triton X-100 cation. The proposed method is available for the stepwise determination of cationic and nonionic surfactants in mixtures.     

利用水下爆炸法评价火炸药爆炸危险性的研究

本文提供了一种测定火炸药冲击感度,并根据测定值判定其冲击爆炸危险性的新方法测定水下爆炸气泡能法。通过对30几种炸药的试用,判定的结果与文献报道的用其他方法判定的结果相当好的一致。而且本法的优点还在于同时可得到试样的动、静态威力,操作简便、安全、噪音小。此外,利用本试验法还探讨了炸药形态、惰性介质(水)对冲击感度的影响。这些对于处理炸药时应如何采取安全对策具有指导意义。     

Regioselective Nucleophilic Functionalization of Antiaromatic Nickel(II) Norcorroles

Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3‐cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO–LUMO gap and enhanced the near IR absorption property.     

Determination of cyanide in blood by electrospray ionization tandem mass spectrometry after direct injection of dicyanogold

An electrospray ionization tandem mass spectrometric (ESI-MS-MS) method has been developed for the determination of cyanide (CN^–) in blood. Five microliters of blood was hemolyzed with 50 μL of water, then 5 μL of 1 M tetramethylammonium hydroxide solution was added to raise the pH of the hemolysate and to liberate CN^– from methemoglobin. CN^– was then reacted with NaAuCl₄ to produce dicyanogold, Au(CN)₂^–, that was extracted with 75 μL of methyl isobutyl ketone. Ten microliters of the extract was injected directly into an ESI-MS-MS instrument and quantification of CN^– was performed by selected reaction monitoring of the product ion CN^– at m/z 26, derived from the precursor ion Au(CN)₂^– at m/z 249. CN^– could be measured in the quantification range of 2.60 to 260 μg/L with the limit of detection at 0.56 μg/L in blood. This method was applied to the analysis of clinical samples and the concentrations of CN^– in the blood were as follows: 7.13 ± 2.41 μg/L for six healthy non-smokers, 3.08 ± 1.12 μg/L for six CO gas victims, 730 ± 867 μg for 21 house fire victims, and 3,030 ± 97 μg/L for a victim who ingested NaCN. The increase of CN^– in the blood of a victim who ingested NaN₃ was confirmed using MS-MS for the first time, and the concentrations of CN^– in the blood, gastric content and urine were 78.5 ± 5.5, 11.8 ± 0.5, and 11.4 ± 0.8 μg/L, respectively.     

Novel synthesis of a unique helical quinone derivative by coupling reaction of 2-hydroxybenzo[c]phenanthrene

Oxidative coupling reaction of both 3-hydroxychrysene and 2-hydroxybenzo[c]phenanthrene by using Cu(NO₃)₂-3H₂O under atmospheric air is described. The former gave the aimed coupled biaryl derivative. However, the latter gave a further oxidized helical quinone derivative. The unique helical structure was characterized by X-ray and NMR analysis.     

Clinical application of extracellular fluid measurement using 35S-sodium sulfate (author's transl)

ECF (extracellular fluid volume) was measured by 35S-sodium sulfate and the same time value of PV (plasma volume) was determined by 131I-RISA in each subject. In normal ECF was an average of 181 ml/kg, 6.21 l/m2 and PV was 49.1 ml/kg, 1.69 l/m2. Both values of ECF and PV in essential hypertension were almost the same as those in normal. In congestive heart failure ECF was 232 ml/kg, 7.51 l/m2 and PV was 55.8 ml/kg, 1.80 l/m2. In the patients with ascites or edema, ECF was 256 ml/kg, 8.69 l/m2 and PV was 53.0 ml/kg, 1.79 l/m2. The results of the measurement by the two compounds also corresponded to the conditions of the patients who showed electrolytes disorders (ACTH deficiency, SIADH) and was improved by treatment.     

Permeability to oxygen of poly(methyl methacrylate) films containing silane-treated glass flakes

Permeability to oxygen of poly(methyl methacrylate) (PMMA) films containing glass flakes (GF) was investigated. The glass flakes were treated with five kinds of silanes and K₂Cr₂O₇-H₂SO₄ solution to improve the affinity with PMMA. The permeability curves were classified into five representative types, which depend on the pretreatment of the glass flakes and the type of silane used as a coupling agent. The factors which influence permeability were studied from the point of view of permeative retardation with the aid of several methods, such as determination of the apparent density of the glass flakes treated with the silanes, the shearing and tensile strength of the PMMA films containing the glass flakes, ESR spectra of films irradiated by γ-rays, and x-ray diffraction patterns of the films. It was found that the three very effective methods to retard the permeability are (a) pretreatment of the glass flakes with NaOH, (b) treatment with γ-methacryloxypropyltrimethoxysilane or ditrimethylsiloxymethylsilane, and (c) heat pressing of the films. The lowest permeability constant which was attained in this study was about one-eighth that with PMMA alone.     

DMPM (3,4-dimethoxybenzyl) protecting group for hydroxy function more readily removable than MPM (P-methoxybenzyl) protecting group by DDQ oxidation

The DMPM (3,4-dimethoxybenzyl) protection for hydroxy function was deprotected more readily than the MPM (p-methoxybenzyl) protection by DDQ oxidation under neutral conditions, and applied to the synthesis of some synthons to macrolide and polyether antibiotics.