WordNet

a coenzyme important in respiration in the Krebs cycle (同)thiamine_pyrophosphate
a salt or ester of pyrophosphoric acid

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vitaminB1

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2016/03/28 04:35:32」(JST)

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Thiamine pyrophosphate (TPP or ThPP), or thiamine diphosphate (ThDP), or cocarboxylase^[1] is a thiamine (vitamin B₁) derivative which is produced by the enzyme thiamine diphosphokinase. Thiamine pyrophosphate is a cofactor that is present in all living systems, in which it catalyzes several biochemical reactions. It was first discovered as an essential nutrient (vitamin) in humans through its link with the peripheral nervous system disease Beriberi, which results from a deficiency of thiamine in the diet.^[2]

TPP works as a coenzyme in many enzymatic reactions, such as:

Pyruvate dehydrogenase complex^[3]
Pyruvate decarboxylase in ethanol fermentation
Alpha-ketoglutarate dehydrogenase complex
Branched-chain amino acid dehydrogenase complex
2-hydroxyphytanoyl-CoA lyase
Transketolase

Chemistry

The "ylide form" of TPP.

Chemically, TPP consists of a pyrimidine ring which is connected to a thiazole ring, which is in turn connected to a pyrophosphate (diphosphate) functional group.

The part of TPP molecule that is most commonly involved in reactions is the thiazole ring, which contains nitrogen and sulfur. Thus, the thiazole ring is the "reagent portion" of the molecule. The C2 of this ring is capable of acting as an acid by donating its proton and forming a carbanion. Normally, reactions that form carbanions are highly unfavorable, but the positive charge on the tetravalent nitrogen just adjacent to the carbanion stabilizes the negative charge, making the reaction more favorable. (A compound with positive and negative charges on adjacent atoms is called an ylid or ylide, so sometimes the carbanion form of TPP is referred to as the "ylid form".^[2]^[4]

Reaction mechanisms

In several reactions, including that of pyruvate dehydrogenase, alpha-ketoglutarate dehydrogenase, and transketolase, TPP catalyses the reversible decarboxylation reaction (aka cleavage of a substrate compound at a carbon-carbon bond connecting a carbonyl group to an adjacent reactive group—usually a carboxylic acid or an alcohol). It achieves this in four basic steps:

The carbanion of the TPP ylid nucleophilically attacks the carbonyl group on the substrate. (This forms a single bond between the TPP and the substrate.)
The target bond on the substrate is broken, and its electrons are pushed towards the TPP. This creates a double bond between the substrate carbon and the TPP carbon and pushes the electrons in the N-C double bond in TPP entirely onto the nitrogen atom, reducing it from a positive to neutral form.
In what is essentially the reverse of step two, the electrons push back in the opposite direction forming a new bond between the substrate carbon and another atom. (In the case of the decarboxylases, this creates a new carbon-hydrogen bond. In the case of transketolase, this attacks a new substrate molecule to form a new carbon-carbon bond.)
In what is essentially the reverse of step one, the TPP-substrate bond is broken, reforming the TPP ylid and the substrate carbonyl.

The TPP thiazolium ring can be deprotonated at C2 to become an ylid.
A full view of TPP. The arrow indicates the acidic proton.

References

^ Pietrzak I (1995). "[Vitamin disturbances in chronic renal insufficiency. I. Water soluble vitamins]". Przegla̧D Lekarski (in Polish) 52 (10): 522–5. PMID 8834846. |access-date= requires |url= (help)
^ ^a ^b Pavia, Donald L., Gary M. Lampman, George S. Kritz, Randall G. Engel (2006). Introduction to Organic Laboratory Techniques (4th Ed.). Thomson Brooks/Cole. pp. 304–5. ISBN 978-0-495-28069-9.
^ "PDBs for Biochemistry". Georgia State University. Retrieved 2009-02-07.
^ Voet, Donald; Judith Voet; Charlotte Pratt (2008). Fundamentals of Biochemistry. John Wiley & Sons Inc. p. 508. ISBN 978-0-470-12930-2.

External links

UIC.edu

UpToDate Contents

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1. 持続的なアルコール依存症患者における栄養状態 nutritional status in patients with sustained heavy alcohol use
2. ウェルニッケ脳症 wernickes encephalopathy
3. 水溶性ビタミンの概要 overview of water soluble vitamins
4. アルコール性肝炎：自然経過およびマネージメント alcoholic hepatitis natural history and management
5. 小児における後天性末梢性ニューロパチーの概要 overview of acquired peripheral neuropathies in children

English Journal

The human colonic thiamine pyrophosphate transporter (hTPPT) is a glycoprotein and N-linked glycosylation is important for its function.

Nabokina SM1, Subramanian VS1, Said HM2.
Biochimica et biophysica acta.Biochim Biophys Acta.2016 Apr;1858(4):866-71. doi: 10.1016/j.bbamem.2016.01.028. Epub 2016 Jan 30.
The recently identified human thiamine pyrophosphate transporter (hTPPT; product of the SLC44A4 gene) is responsible for absorption of the microbiota-generated TPP in the large intestine. The hTPPT is highly expressed in the colon, but not in other regions of the intestinal tract and is localized ex
PMID 26828122

Role of riboswitches in gene regulation and their potential for algal biotechnology.

Nguyen GT1, Scaife MA1, Helliwell KE1, Smith AG1.
Journal of phycology.J Phycol.2016 Mar 31. doi: 10.1111/jpy.12416. [Epub ahead of print]
Riboswitches are regulatory elements in messenger RNA to which specific ligands can bind directly in the absence of proteins. Ligand binding alters the mRNA secondary structure, thereby affecting expression of the encoded protein. Riboswitches are widespread in prokaryotes, with over 20 different ef
PMID 27037670

Thiamine synthesis regulates the fermentation mechanisms in the fungus Aspergillus nidulans.

Shimizu M1,2, Masuo S1, Itoh E1, Zhou S1, Kato M2, Takaya N1.
Bioscience, biotechnology, and biochemistry.Biosci Biotechnol Biochem.2016 Mar 11:1-8. [Epub ahead of print]
Thiamine pyrophosphate (TPP) is a critical cofactor and its biosynthesis is under the control of TPP availability. Here we disrupted a predicted thiA gene of the fungus Aspergillus nidulans and demonstrated that it is essential for synthesizing cellular thiamine. The thiamine riboswitch is a post-tr
PMID 26967817

Japanese Journal

Classification of hypo and hyperthiaminosis

Ihara Hiroshi,Igarashi Hiroaki,Kakinoki Takashi [他]
International journal of analytical bio-science 1(2), 45-49, 2013-12
NAID 40019919626

Construction of a thiamine pyrophosphate high-producing strain of Aspergillus oryzae by overexpression of three genes involved in thiamine biosynthesis(GENETICS, MOLECULAR BIOLOGY, AND GENE ENGINEERING)

Tokui Misato,Kubodera Takafumi,Gomi Katsuya [他],Yamashita Nobuo,Nishimura Akira
Journal of bioscience and bioengineering 111(4), 388-390, 2011-04
… We have found a gene (thiP) encoding thiamine pyrophosphokinase (TPK) in the Aspergillus oryzae genome. … No riboswitch-like region was found in the upstream region of thiP, although it was repressed probably by thiamine pyrophosphate (TPP) as well as thiA and nmtA, which are strictly regulated by TPP-riboswitch sequence. …
NAID 110008607489

Whole blood concentration of thiamine diphosphate requires correction for red blood cell count in the nutritional assessment of thiamine status

Ihara Hiroshi,Suzuki Toshikazu,Hashizume Naotaka
生物試料分析 = Journal of analytical bio-science 34(3), 218-222, 2011
NAID 40019884141

Related Pictures

★リンクテーブル★

リンク元	「ビタミンB1」「チアミン二リン酸」「コカルボキシラーゼ」「TPP」「チアミンピロリン酸」
関連記事	「pyrophosphate」「thiamin」

「ビタミンB1」

Thiamine pyrophosphate
Names
	IUPAC name 2-[3-[(4-amino-2-methylpyrimidin-5-yl)methyl]-4-methyl-1,3-thiazol-3-ium-5-yl]ethyl phosphono hydrogen phosphate
	Other names Thiamine diphosphate
Identifiers
CAS Number	154-87-0
ChemSpider	10670483
Jmol interactive 3D	Image
MeSH	Thiamine+pyrophosphate
PubChem	1132
UNII	Q57971654Y
	InChI InChI=1S/C12H17N4OS.ClH.H4O7P2/c1-8-11(3-4-17)18-7-16(8)6-10-5-14-9(2)15-12(10)13;;1-8(2,3)7-9(4,5)6/h5,7,17H,3-4,6H2,1-2H3,(H2,13,14,15);1H;(H2,1,2,3)(H2,4,5,6)/q+1;;/p-1 Key: NBSUTVXQOGUTJX-UHFFFAOYSA-M ; InChI=1/C12H17N4OS.ClH.H4O7P2/c1-8-11(3-4-17)18-7-16(8)6-10-5-14-9(2)15-12(10)13;;1-8(2,3)7-9(4,5)6/h5,7,17H,3-4,6H2,1-2H3,(H2,13,14,15);1H;(H2,1,2,3)(H2,4,5,6)/q+1;;/p-1 Key: NBSUTVXQOGUTJX-REWHXWOFAB ;
	SMILES [Cl-].OP(=O)(O)OP(O)(O)=O.Cc2nc(N)c(C[n+]1csc(CCO)c1C)cn2 ;
Properties
Chemical formula	C12H19N4O7P2S+
Molar mass	425.314382 g/mol
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	verify (what is ?)
	Infobox references

　　[★]

英: vitamine B1
同: チアミン thiamine、塩酸チアミン thiamine hydrochloride、ビタミンB1塩酸塩、アノイリン aneurine
商: アミグランド、パレセーフ、ビーフリード
関: ビタミン、チアミン二リン酸 thiamine pyrophosphate チアミンピロリン酸 TPP

水溶性ビタミン

機能

補酵素

体内でリン酸化されてピロリン酸エステルであるチアミン二リン酸(TPP)となり機能する。
α-ケト酸の酸化的脱炭酸反応(oxidative decarboxylation)、ケトール形成反応に関わる。
1. 解糖系からTCA回路を繋ぐ反応：チアミン二リン酸はピルビン酸デヒドロゲナーゼに非共有結合して、以下の脱炭酸反応を触媒

ピルビン酸 + CoASH + NAD⁺　－(ピルビン酸デヒドロゲナーゼ)→　アセチルCoA + NADH + CO₂

2. TCA回路の反応

α-ケトグルタル酸 + CoASH + NAD⁺ －(α-keto glutarate dehydrogenase)→　サクシニルCoA + NADH + CO₂

3. branched-chain ketoacid dehyrogenase: involved in metabolism of branched-chain amino acid; deficiency results in maple syrup urine disease

4. transketolase; hexose monophosphate shunt

5. 酵母などではアルコール発酵を行うピルビン酸デカルボキシラーゼ(ピルビン酸からCO₂を除去してアセトアルデヒドを産生)の補酵素として重要

ピルビン酸－(ピルビン酸デカルボキシラーゼ)→アセトアルデヒド + CO₂

臨床関連

ビタミンB₁欠乏症

「チアミン二リン酸」

　　[★]

英: thiamin diphosphate,TDP, thiamine pyrophosphate, TPP
関: ビタミンB₁ = チアミン; ピルビン酸デヒドロゲナーゼ、ビタミンB1、チアミン thiamin; コカルボキシラーゼ

[show details]

en

thiamine pyrophosphate : 約 134,000 件
thiamin diphosphate : 約 195,000 件

ja

thiamine pyrophosphate : 約 2,420 件
thiamin diphosphate : 約 1,600 件
チアミンピロリン酸 : 約 51,800 件
チアミン二リン酸 : 約 47,300 件

「コカルボキシラーゼ」

　　[★]

英: cocarboxylase
同: チアミンピロリン酸 thiamine pyrophosphate TPP、チアミン二リン酸 thiamine diphosphate、ジホスホチアミン diphosphothiamine、アノイリンピロリン酸 aneurine pyrophosphate
商: アリチラーゼ、プロフィット
関: 活性チアミン誘導体、脚気

「TPP」

　　[★]

「チアミンピロリン酸」

　　[★]

英: thiamine pyrophosphate, TPP
同: チアミンニリン酸
関: コカルボキシラーゼ

「pyrophosphate」

　　[★] ピロリン酸、二リン酸

関: bisphosphate、diphosphate、diphosphoric acid、PPi

「thiamin」

　　[★] ビタミンB1、チアミン, thiamine

[pmid8834846-1] Pietrzak I (1995). "[Vitamin disturbances in chronic renal insufficiency. I. Water soluble vitamins]". Przegla̧D Lekarski (in Polish) 52 (10): 522–5. PMID 8834846. |access-date= requires |url= (help)

[Pavia-2] Pavia, Donald L., Gary M. Lampman, George S. Kritz, Randall G. Engel (2006). Introduction to Organic Laboratory Techniques (4th Ed.). Thomson Brooks/Cole. pp. 304–5. ISBN 978-0-495-28069-9.

[GSU-3] "PDBs for Biochemistry". Georgia State University. Retrieved 2009-02-07.

[Voet-4] Voet, Donald; Judith Voet; Charlotte Pratt (2008). Fundamentals of Biochemistry. John Wiley & Sons Inc. p. 508. ISBN 978-0-470-12930-2.

匿名

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案内

案内

thiamine pyrophosphate