WordNet

a chemical agent for use in chemical reactions

PrepTutorEJDIC

(化学実験の)試薬

Wikipedia preview

出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2016/10/03 05:54:05」(JST)

wiki en

The structure of the fuchsin dye.

The Schiff test is an early organic chemistry name reaction developed by Hugo Schiff,^[1] and is a relatively general chemical test for detection of many organic aldehydes that has also found use in the staining of biological tissues.^[2] The Schiff reagent is the reaction product of a dye formulation such as fuchsin and sodium bisulfite; pararosaniline (which lacks an aromatic methyl group) and new fuchsin (which is uniformly mono-methylated ortho to the dye's amine functionalities) are dye alternatives with comparable detection chemistry.

In its use as a qualitative test for aldehydes, the unknown sample is added to the decolorized Schiff reagent; when aldehyde is present a characteristic magenta color develops. Schiff-type reagents are used for various biological tissue staining methods, e.g. Feulgen stain and periodic acid-Schiff stain. Human skin also contains aldehyde functional groups in the termini of saccharides and so is stained as well.

Mechanism

Fuchsin solutions appear colored due to the visible wavelength absorbance of its central quinoid structure—see also for example viologen —but are "discolorized" upon sulfonation of the dye at its central carbon atom by sulfurous acid or its conjugate base, bisulfite.^{[citation needed]} This reaction disrupts the otherwise favored delocalized extended pi-electron system and resonance in the parent molecule.^{[citation needed]}

The structure of the "decolorized" Schiff reagent.

The further reaction of the Schiff reagent with aldehydes is complex with several research groups reporting multiple reaction products with model compounds. In the currently accepted mechanism, the pararosaniline and bisulfite combine to yield the "decolorized" adduct with sulfonation at the central carbon as described and shown. The free, uncharged aromatic amine groups then react with the aldehyde being tested to form two aldimine groups; these groups have also been named for their discoverer as Schiff bases (azomethines), with the usual carbinolamine (hemiaminal) intermediate being formed and dehydrated en route to the Schiff base. These electrophilic aldimine groups then react with further bisulfite, and the Ar-NH-CH(R)-SO₃⁻ product (and other resonance-stabilized species in equilibrium with the product) give rise to the magenta color of a positive test.^[3] Prior formation of classical bisulfite adducts of the tested aldehyde may, when the adducts are stable, give rise to false negative tests such as in the case of testing for the aldehydic terminus of glucose.^[4]

Such an imine-mediated mechanism was first proposed by Rumpf in 1935, and experimental evidence was provided by Hardonk and van Duijn in 1964.^[5] Robins, Abrams and Pincock have provided substantial NMR evidence for the mechanism, leading to its general acceptance.^[6] Earlier work from Stoward in 1966 on the whole he agreed with this mechanism.^[7]

A second, earlier mechanism continues to appear in the literature.^[8] The mechanism was proposed by eminent German organic chemist Heinrich Wieland in 1935. Bisulphite was believed to react with the available aromatic amine functional groups to form N-sulfinic acid groups, Ar-NH-SO₂H, followed by reaction with aldehyde to form sulfonamides, Ar-NH-SO₂CH(OH)-R. The 1980 NMR data that allowed visualization of intermediates does not support this mechanism or the sulfonamides as the chromogenic product.^[9]

References

^ Schiff, H (1866) Eine neue Reihe organischen Diaminen, Justus Liebigs Ann Chemie 140, 92-137.
^ Histology, cell and tissue biology 5th Ed., 1983 ISBN 0-333-35406-0
^ http://daten.didaktikchemie.uni-bayreuth.de/cnat/fa_paare/schiffsche_probe.htm, accessed 8 March 2013.
^ http://daten.didaktikchemie.uni-bayreuth.de/cnat/fa_paare/schiffsche_probe.htm, accessed 8 March 2013.
^ Hardonk, MJ & Van Duijn, P (1964) The mechanism of the Schiff reaction as studied with histochemical model systems, J. Histochem. Cytochem. 12:748-751.
^ Robins, JH, Abrams, GD & Pincock, JA (1980) The structure of Schiff reagent aldehyde adducts and the mechanism of the Schiff reaction as determined by nuclear magnetic resonance spectroscopy, Can. J. Chem. 58(4): 339-347.
^ Stoward, PJ (1966) Some comments on the mechanism of the Schiff reaction, J. Histochem. Cytochem. 14:681-683.
^ Histochemistry, theoretical and applied 4th Ed. 1985 ISBN 0-443-02997-0 Note: the depiction of the sulfonic acid mechanism in this edition contains an error as the aldehyde R group is bonded to nitrogen and not to its carbon neighbor
^ Robins, JH, Abrams, GD & Pincock, JA (1980) The structure of Schiff reagent aldehyde adducts and the mechanism of the Schiff reaction as determined by nuclear magnetic resonance spectroscopy, Can. J. Chem. 58(4): 339-347.

External links

What is Schiff's reagent?

UpToDate Contents

全文を閲覧するには購読必要です。 To read the full text you will need to subscribe.

1. 成人における肺胞蛋白症の診断および治療 diagnosis and treatment of pulmonary alveolar proteinosis in adults
2. 爪真菌症 onychomycosis
3. ウィップル病 whipples disease
4. 嚢胞性線維症：肝胆道系疾患 cystic fibrosis hepatobiliary disease
5. 珪肺症 silicosis

English Journal

Visualizing Compound Distribution during Zebrafish Embryo Development: The Effects of Lipophilicity and DMSO.

de Koning C1, Beekhuijzen M1, Tobor-Kapłon M1, de Vries-Buitenweg S1, Schoutsen D1, Leeijen N1, van de Waart B1, Emmen H1.
Birth defects research. Part B, Developmental and reproductive toxicology.Birth Defects Res B Dev Reprod Toxicol.2015 Dec 11. doi: 10.1002/bdrb.21166. [Epub ahead of print]
The predictability of the zebrafish embryo model is highly influenced by internal exposure of the embryo/larva. As compound uptake is likely to be influenced by factors such as lipophilicity, solvent use, and chorion presence, this article focuses on investigating their effects on compound distribut
PMID 26663754

Yi Qi Qing Re Gao formula ameliorates puromycin aminonucleoside-induced nephrosis by suppressing inflammation and apoptosis.

Wen Y1,2,3, Zhan Y4, Liu H5, Zhao T6,7, Yang L8, Zhang H9,10, Dong X11,12, Li P13,14.
BMC complementary and alternative medicine.BMC Complement Altern Med.2015 May 27;15:155. doi: 10.1186/s12906-015-0673-9.
BACKGROUND: Yi Qi Qing Re Gao (YQQRG) formula is a traditional Chinese herbal medicine used to treat chronic nephritis. This study was designed to evaluate the underlying mechanism in the use of YQQRG formula to treat nephrosis induced by puromycin aminonucleoside (PAN).METHODS: Thirty-six male Wist
PMID 26014479

Histological and lectin histochemical studies on the olfactory mucosae of the Korean roe deer, Capreolus pygargus.

Park C1, Ahn M2, Kim J1, Kim S3, Moon C4, Shin T5.
Tissue & cell.Tissue Cell.2015 Apr;47(2):221-7. doi: 10.1016/j.tice.2014.11.002. Epub 2014 Nov 18.
The morphological features of the olfactory mucosae of Korean roe deer, Capreolus pygargus, were histologically studied using the ethmoid turbinates containing the olfactory mucosae from six roe deer (male, 2-3 years old). The ethmoid turbinates were embedded in paraffin, and histochemically evaluat
PMID 25480445

Japanese Journal

溶媒抽出用試薬を導入した新規キレート分離材の合成

國仙久雄
日本イオン交換学会誌 26(1), 1-8, 2015
水溶液中に溶存する金属イオンの効率的捕集を目的として，オクタデシル基を表面修飾したシリカゲル（ODS）上に溶媒抽出で用いた配位子を吸着担持させた分離材および，配位子を担体に化学結合させた分離材を合成した。配位子として，負二価六座配位子のH2Clbbpenまたは，負二価四座配位子のシッフ塩基誘導体を用いた。また，担体として用いた植物繊維による金属イオンの捕集も併せて検討した。H2Clbbpenを吸 …
NAID 130004845705

改良したタバコ煙採取法を含む喫煙防止教育プログラムの検討

勝又聖夫,平田紀美子,小林麻衣子,平田幸代,稲垣弘文,川田智之
日本衛生学雑誌 69(3), 235-241, 2014
… After collection, we performed gas measurement using a gas detection tube and the Schiff reagent method. …
NAID 130004691295

多孔質ガラスを用いたVOCセンサの開発(センサ,デバイス,一般)

丸尾容子,中村二朗,泉克幸
電子情報通信学会技術研究報告. OME, 有機エレクトロニクス 109(359), 57-62, 2010-01-05
多孔質ガラスにシッフ試薬とリン酸若しくは硫酸を含浸させたセンサ素子を作製し,揮発性有機化合物(VOC)の検出の可能性について検討した.各センサ素子は,アルデヒド類,芳香剤として用いられるリモネン,2-メチル-3-ブテン-2-オールに反応し,吸収スペクトルが変化することが明らかになった.同一物質に暴露した場合でもリン酸素子と硫酸素子で可視領域の吸収スペクトルは異なり,目で認識される色も異なることから …
NAID 110008001528