Mono-, di-, tri-, and tetra-substituted fluorotyrosines: New probes for enzymes that use tyrosyl radicals in catalysis

被引：0
|
作者：
Seyedsayamdost, Mohammad R. [1 ]
Reece, Steven Y. [1 ]
Nocera, Daniel G. [1 ]
Stubbe, JoAnne [1 ]
机构：
[1] Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139-4307, United States
来源：
Journal of the American Chemical Society | 1600年 / 128卷 / 05期
关键词：
A set of N-acylated, carboxyamide fluorotyrosine (FnY) analogues [Ac-S-FY-NH2, Ac-3,5-F2Y-NH2, Ac-2,3-F 2Y-NH2, Ac-2,3,5-F3Y-NH2, Ac-2,3,6-F3Y-NH2 and Ac-2,3,5,6-F4Y-NH 2] have been synthesized from their corresponding amino acids to interrogate the detailed reaction mechanism(s) accessible to F nY&bulls in small molecules and in proteins. These Ac-F nY-NH2 derivatives span a pKa range from 5.6 to 8.4 and a reduction potential range of 320 mV in the pH region accessible to most proteins (6-9). DFT electronic-structure calculations capture the observed trends for both the reduction potentials and pKaS. Dipeptides of the methyl ester of 4-benzoyl-L-phenylalanyl-FnYs at pH 4 were examined with a nanosecond laser pulse and transient absorption spectroscopy to provide absorption spectra of FnY&bulls. The EPR spectrum of each F nY&bull has also been determined by UV photolysis of solutions at pH 11 and 77 K. The ability to vary systematically both pKa and radical reduction potential, together with the facility to monitor radical formation with distinct absorption and EPR features, establishes that FnYs will be useful in the study of biological charge-transport mechanisms involving tyrosine. To demonstrate the efficacy of the fluorotyrosine method in unraveling charge transport in complex biological systems, we report the global substitution of tyrosine by 3-fluorotyrosine (3-FY) in the R2 subunit of ribonucleotide reductase (RNR) and present the EPR spectrum along with its simulation of 3-FY122&bull. In the companion paper, we demonstrate the utility of FnYs in providing insight into the mechanism of tyrosine oxidation in biological systems by incorporating them site-specifically at position 356 in the R2 subunit of Escherichia coli RNR. © 2006 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
页码：1569 / 1579
相关论文
共 50 条
  • [1] Mono-, di-, tri-, and tetra-substituted fluorotyrosines: New probes for enzymes that use tyrosyl radicals in catalysis
    Seyedsayamdost, MR
    Reece, SY
    Nocera, DG
    Stubbe, J
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (05) : 1569 - 1579
  • [2] PREPARATION OF MONO-, DI-, TRI-, TETRA-, AND PENTA-ETHYLENEGLYCOLCHLOROHYDRIN
    ABE, Y
    WATANABE, S
    KOGYO KAGAKU ZASSHI, 1961, 64 (07): : 1192 - &
  • [3] Synthesis of new chiral mono-, di-, tri-, and tetraalkylglycolurils
    A. N. Kravchenko
    A. S. Sigachev
    E. Yu. Maksareva
    G. A. Gazieva
    N. S. Trunova
    B. V. Lozhkin
    T. S. Pivina
    M. M. Il’in
    K. A. Lyssenko
    Yu. V. Nelyubina
    V. A. Davankov
    O. V. Lebedev
    N. N. Makhova
    V. A. Tartakovsky
    Russian Chemical Bulletin, 2005, 54 : 691 - 704
  • [4] Synthesis of new chiral mono-, di-, tri-, and tetraalkylglycolurils
    Kravchenko, AN
    Sigachev, AS
    Maksareva, EY
    Gazieva, GA
    Trunova, NS
    Lozhkin, BV
    Pivina, TS
    Il'in, MM
    Lyssenko, KA
    Nelyubina, YV
    Davankov, VA
    Lebedev, OV
    Makhova, NN
    Tartakovsky, VA
    RUSSIAN CHEMICAL BULLETIN, 2005, 54 (03) : 691 - 704
  • [5] Preparation of di-, tri-, and tetra-substituted functionalized ferrocenes via magnesium organometallics
    Stoll, Armin H.
    Mayer, P.
    Knochel, Paul
    ORGANOMETALLICS, 2007, 26 (27) : 6694 - 6697
  • [6] A rapid and large volume synthesis of mono-, di-, tri-, and tetra-substituted imidazole derivatives via ultrasonic radiation-driven technique
    Shaikh, Mohd Sayeed
    Kale, Mayura A.
    Zehravi, Mehrukh
    Unnisa, Aziz
    Haque, M. Akiful
    Kumar, Kusuma Praveen
    Khan, Sharuk L.
    Ali, Syed Sarfaraz
    Siddiqui, Falak A.
    Emran, Talha Bin
    Abdelrahim, Elrashed
    Khandaker, Mayeen Uddin
    RADIATION EFFECTS AND DEFECTS IN SOLIDS, 2024, 179 (3-4): : 431 - 450
  • [7] Tensammetry of homogeneous mono-, di- and tri- ethoxydodecylethers
    Borkowska, Magdalena
    Szymanski, Andrzej
    Lukaszewski, Zenon
    CHEMIA ANALITYCZNA, 2007, 52 (06): : 1059 - 1069
  • [8] Coprecipitation of Mono-, Di-, Tri-, Tetra- and Hexavalent Ions with Na-Polyuranates
    Diaz, Arocas, P. D.
    Carcia-Serrano, J.
    QuiOones, J.
    Geckeis, H.
    1996, (74)
  • [9] Coprecipitation of mono-, di-, tri-, tetra- and hexavalent ions with Na-polyuranates
    Arocas, PD
    GarciaSerrano, J
    Quinones, J
    Geckeis, H
    Grambow, B
    RADIOCHIMICA ACTA, 1996, 74 : 51 - 58
  • [10] Mono-, di-, tri- and tetraphosphatriafulvenes:: Electronic structure and aromaticity
    Holtzl, Tibor
    Nguyen, Minh Tho
    Veszpremi, Tamas
    JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2007, 811 (1-3): : 27 - 35
12345